EP3731958B1 - Surfactant compositions and uses as inverters - Google Patents
Surfactant compositions and uses as inverters Download PDFInfo
- Publication number
- EP3731958B1 EP3731958B1 EP18842503.7A EP18842503A EP3731958B1 EP 3731958 B1 EP3731958 B1 EP 3731958B1 EP 18842503 A EP18842503 A EP 18842503A EP 3731958 B1 EP3731958 B1 EP 3731958B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- polymer
- water
- inversion
- alkyl
- activator
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
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- 239000004094 surface-active agent Substances 0.000 title claims description 188
- 239000000203 mixture Substances 0.000 title claims description 125
- 229920000642 polymer Polymers 0.000 claims description 313
- 229910052739 hydrogen Inorganic materials 0.000 claims description 65
- 239000001257 hydrogen Substances 0.000 claims description 65
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 58
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 54
- 125000000217 alkyl group Chemical group 0.000 claims description 52
- 239000003921 oil Substances 0.000 claims description 48
- 239000000839 emulsion Substances 0.000 claims description 43
- 125000003118 aryl group Chemical group 0.000 claims description 40
- 239000007762 w/o emulsion Substances 0.000 claims description 40
- -1 polyoxyethylene Polymers 0.000 claims description 39
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 32
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 31
- 239000012071 phase Substances 0.000 claims description 28
- 239000007864 aqueous solution Substances 0.000 claims description 19
- 229920006395 saturated elastomer Polymers 0.000 claims description 19
- 150000002431 hydrogen Chemical group 0.000 claims description 18
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 17
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 15
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 13
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- 229910019142 PO4 Inorganic materials 0.000 claims description 12
- 239000003995 emulsifying agent Substances 0.000 claims description 12
- 239000010452 phosphate Substances 0.000 claims description 12
- 125000000129 anionic group Chemical group 0.000 claims description 10
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 239000004359 castor oil Substances 0.000 claims description 8
- 235000019438 castor oil Nutrition 0.000 claims description 8
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 8
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical class CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims description 8
- 239000008346 aqueous phase Substances 0.000 claims description 7
- 229920000847 nonoxynol Polymers 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 6
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- MUHFRORXWCGZGE-KTKRTIGZSA-N 2-hydroxyethyl (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCCO MUHFRORXWCGZGE-KTKRTIGZSA-N 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 229920000223 polyglycerol Polymers 0.000 claims description 5
- 150000003333 secondary alcohols Chemical class 0.000 claims description 5
- 239000000375 suspending agent Substances 0.000 claims description 5
- XUJLWPFSUCHPQL-UHFFFAOYSA-N 11-methyldodecan-1-ol Chemical compound CC(C)CCCCCCCCCCO XUJLWPFSUCHPQL-UHFFFAOYSA-N 0.000 claims description 4
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 4
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 4
- 239000004435 Oxo alcohol Substances 0.000 claims description 4
- 229920002690 Polyoxyl 40 HydrogenatedCastorOil Polymers 0.000 claims description 4
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 4
- 229930006000 Sucrose Natural products 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 125000002091 cationic group Chemical group 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 claims description 4
- 229960001231 choline Drugs 0.000 claims description 4
- BOWVQLFMWHZBEF-KTKRTIGZSA-N oleoyl ethanolamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)NCCO BOWVQLFMWHZBEF-KTKRTIGZSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- CNTXYLCDFKRSRI-UHFFFAOYSA-N phosphoric acid;1-tridecoxytridecane Chemical compound OP(O)(O)=O.CCCCCCCCCCCCCOCCCCCCCCCCCCC CNTXYLCDFKRSRI-UHFFFAOYSA-N 0.000 claims description 4
- 229920002401 polyacrylamide Polymers 0.000 claims description 4
- 150000003138 primary alcohols Chemical class 0.000 claims description 4
- 239000000600 sorbitol Substances 0.000 claims description 4
- 239000005720 sucrose Substances 0.000 claims description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 3
- NLBSQHGCGGFVJW-UHFFFAOYSA-N 2-carboxyethylphosphonic acid Chemical compound OC(=O)CCP(O)(O)=O NLBSQHGCGGFVJW-UHFFFAOYSA-N 0.000 claims description 3
- GUXRZQZCNOHHDO-UHFFFAOYSA-N 2-phosphonopropanoic acid Chemical compound OC(=O)C(C)P(O)(O)=O GUXRZQZCNOHHDO-UHFFFAOYSA-N 0.000 claims description 3
- UYRFPODVSLYSCO-UHFFFAOYSA-N 4-phosphonobutanoic acid Chemical compound OC(=O)CCCP(O)(O)=O UYRFPODVSLYSCO-UHFFFAOYSA-N 0.000 claims description 3
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims description 3
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 claims description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims description 3
- 229960000878 docusate sodium Drugs 0.000 claims description 3
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 239000004310 lactic acid Substances 0.000 claims description 3
- 235000014655 lactic acid Nutrition 0.000 claims description 3
- 239000001630 malic acid Substances 0.000 claims description 3
- 235000011090 malic acid Nutrition 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 claims description 3
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical compound OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims 1
- 239000004584 polyacrylic acid Substances 0.000 claims 1
- 239000012190 activator Substances 0.000 description 177
- 230000003213 activating effect Effects 0.000 description 100
- 239000004908 Emulsion polymer Substances 0.000 description 36
- 102000018779 Replication Protein C Human genes 0.000 description 23
- 108010027647 Replication Protein C Proteins 0.000 description 23
- 239000000243 solution Substances 0.000 description 19
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- 239000012267 brine Substances 0.000 description 13
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- 239000000178 monomer Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- HFRUPPHPJRZOCM-UHFFFAOYSA-N 4-octoxyphenol Chemical compound CCCCCCCCOC1=CC=C(O)C=C1 HFRUPPHPJRZOCM-UHFFFAOYSA-N 0.000 description 8
- 239000003153 chemical reaction reagent Substances 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 8
- 150000002430 hydrocarbons Chemical group 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 239000000523 sample Substances 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 6
- 238000010926 purge Methods 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 229920003169 water-soluble polymer Polymers 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- 125000000623 heterocyclic group Chemical group 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 239000013535 sea water Substances 0.000 description 5
- 239000008399 tap water Substances 0.000 description 5
- 235000020679 tap water Nutrition 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 125000003710 aryl alkyl group Chemical group 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 239000003209 petroleum derivative Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- FVEFRICMTUKAML-UHFFFAOYSA-M sodium tetradecyl sulfate Chemical compound [Na+].CCCCC(CC)CCC(CC(C)C)OS([O-])(=O)=O FVEFRICMTUKAML-UHFFFAOYSA-M 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- OBRHFMNBWAWJRM-UHFFFAOYSA-N (prop-2-enoylamino) 2-methylpropane-2-sulfonate Chemical compound CC(C)(C)S(=O)(=O)ONC(=O)C=C OBRHFMNBWAWJRM-UHFFFAOYSA-N 0.000 description 3
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 description 3
- VMKOFRJSULQZRM-UHFFFAOYSA-N 1-bromooctane Chemical compound CCCCCCCCBr VMKOFRJSULQZRM-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 125000001246 bromo group Chemical group Br* 0.000 description 3
- 239000001110 calcium chloride Substances 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- 238000005352 clarification Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000005553 drilling Methods 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000008235 industrial water Substances 0.000 description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 125000002950 monocyclic group Chemical group 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920001983 poloxamer Polymers 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000001593 sorbitan monooleate Substances 0.000 description 3
- 235000011069 sorbitan monooleate Nutrition 0.000 description 3
- 229940035049 sorbitan monooleate Drugs 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 125000000547 substituted alkyl group Chemical group 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000007832 Na2SO4 Substances 0.000 description 2
- 229920002257 Plurafac® Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 125000002619 bicyclic group Chemical group 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000000872 buffer Substances 0.000 description 2
- 235000011148 calcium chloride Nutrition 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000013505 freshwater Substances 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- HGEMCUOAMCILCP-UHFFFAOYSA-N isotridecane Natural products CCCCCCCCCCC(C)C HGEMCUOAMCILCP-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- XUXNAKZDHHEHPC-UHFFFAOYSA-M sodium bromate Chemical compound [Na+].[O-]Br(=O)=O XUXNAKZDHHEHPC-UHFFFAOYSA-M 0.000 description 2
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 2
- 229940001584 sodium metabisulfite Drugs 0.000 description 2
- 235000010262 sodium metabisulphite Nutrition 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 125000003107 substituted aryl group Chemical group 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 239000003981 vehicle Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical class OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- CZSRXHJVZUBEGW-UHFFFAOYSA-N 1,2-thiazolidine Chemical compound C1CNSC1 CZSRXHJVZUBEGW-UHFFFAOYSA-N 0.000 description 1
- 125000004214 1-pyrrolidinyl group Chemical group [H]C1([H])N(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- IEORSVTYLWZQJQ-UHFFFAOYSA-N 2-(2-nonylphenoxy)ethanol Chemical compound CCCCCCCCCC1=CC=CC=C1OCCO IEORSVTYLWZQJQ-UHFFFAOYSA-N 0.000 description 1
- KWVPFECTOKLOBL-KTKRTIGZSA-N 2-[(z)-octadec-9-enoxy]ethanol Chemical compound CCCCCCCC\C=C/CCCCCCCCOCCO KWVPFECTOKLOBL-KTKRTIGZSA-N 0.000 description 1
- IDOQDZANRZQBTP-UHFFFAOYSA-N 2-[2-(2,4,4-trimethylpentan-2-yl)phenoxy]ethanol Chemical compound CC(C)(C)CC(C)(C)C1=CC=CC=C1OCCO IDOQDZANRZQBTP-UHFFFAOYSA-N 0.000 description 1
- 125000004485 2-pyrrolidinyl group Chemical group [H]N1C([H])([H])C([H])([H])C([H])([H])C1([H])* 0.000 description 1
- 125000004575 3-pyrrolidinyl group Chemical group [H]N1C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- JYCQQPHGFMYQCF-UHFFFAOYSA-N 4-tert-Octylphenol monoethoxylate Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(OCCO)C=C1 JYCQQPHGFMYQCF-UHFFFAOYSA-N 0.000 description 1
- XZIIFPSPUDAGJM-UHFFFAOYSA-N 6-chloro-2-n,2-n-diethylpyrimidine-2,4-diamine Chemical compound CCN(CC)C1=NC(N)=CC(Cl)=N1 XZIIFPSPUDAGJM-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229930194542 Keto Natural products 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N Nitrogen dioxide Chemical compound O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 101100152661 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) TDA9 gene Proteins 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
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- 125000003016 chromanyl group Chemical group O1C(CCC2=CC=CC=C12)* 0.000 description 1
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- 125000004282 imidazolidin-2-yl group Chemical group [H]N1C([H])([H])C([H])([H])N([H])C1([H])* 0.000 description 1
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- 125000003387 indolinyl group Chemical group N1(CCC2=CC=CC=C12)* 0.000 description 1
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- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 1
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- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
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- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
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- 125000004194 piperazin-1-yl group Chemical group [H]N1C([H])([H])C([H])([H])N(*)C([H])([H])C1([H])[H] 0.000 description 1
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- 125000000587 piperidin-1-yl group Chemical group [H]C1([H])N(*)C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
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- 125000004483 piperidin-3-yl group Chemical group N1CC(CCC1)* 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
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- 125000003072 pyrazolidinyl group Chemical group 0.000 description 1
- 125000000719 pyrrolidinyl group Chemical group 0.000 description 1
- 125000004621 quinuclidinyl group Chemical group N12C(CC(CC1)CC2)* 0.000 description 1
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- 239000012966 redox initiator Substances 0.000 description 1
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- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
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- 229940035044 sorbitan monolaurate Drugs 0.000 description 1
- 239000001587 sorbitan monostearate Substances 0.000 description 1
- 235000011076 sorbitan monostearate Nutrition 0.000 description 1
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- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001631 strontium chloride Inorganic materials 0.000 description 1
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 description 1
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- 229910052717 sulfur Inorganic materials 0.000 description 1
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000004192 tetrahydrofuran-2-yl group Chemical group [H]C1([H])OC([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 description 1
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 1
- XFLNVMPCPRLYBE-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate;tetrahydrate Chemical compound O.O.O.O.[Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O XFLNVMPCPRLYBE-UHFFFAOYSA-J 0.000 description 1
- 125000001984 thiazolidinyl group Chemical group 0.000 description 1
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- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 125000006168 tricyclic group Chemical group 0.000 description 1
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- 238000004457 water analysis Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000002349 well water Substances 0.000 description 1
- 235000020681 well water Nutrition 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
- C07C43/23—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing hydroxy or O-metal groups
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/547—Tensides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2612—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aromatic or arylaliphatic hydroxyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
- C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
- C08J3/095—Oxygen containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/017—Mixtures of compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/42—Ethers, e.g. polyglycol ethers of alcohols or phenols
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/02—Well-drilling compositions
- C09K8/32—Non-aqueous well-drilling compositions, e.g. oil-based
- C09K8/36—Water-in-oil emulsions
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/584—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific surfactants
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/588—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific polymers
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/50—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by form
Definitions
- Surfactants capable of releasing and/or dissolving polymers to form water-soluble or water-dispersible polymer solutions are disclosed.
- polymer compositions containing a water-in-oil emulsion comprising the surfactant are provided and can be used, for example, in methods of dissolving a polymer.
- These surfactants and polymer compositions can be used in various industries including for water clarification, papermaking, sewage and industrial water treatment, drilling mud stabilizers, and enhanced oil recovery.
- water-soluble or water-dispersible polymers can be used in a variety of commercial applications. These polymers are commercially available as powders, finely-divided solids, or water-in-oil emulsion polymers that require the polymer to be dissolved in water. While the polymers are water-soluble or water-dispersible, it can be difficult to prepare solutions or homogeneous dispersions because of slow dissolution or slow dispersion into the water. Further, polymers can clump or remain as agglomerates on contact with water. Although these clumps eventually dissolve or disperse using agitation, it can be impractical to agitate the solution for a sufficiently long time to obtain complete dissolution of the polymer particles.
- surfactants can invert and/or activate water-in-oil emulsion polymers to aid the dissolution and dispersion of those polymers.
- Such inversion surfactants can be used to increase the dissolution of various emulsion polymers so the time for dissolution and degree of dissolution of the polymer is increased.
- an inversion surfactant can be used.
- Ethoxylated alkylphenols and alkylphenol-formaldehyde resins, particularly containing nonylphenol moiety as one of the building blocks have been used in the industry as one class of inversion surfactants.
- GB2146260 discloses water-in-oil emulsions comprising an inverting surfactant like octylphenol ethoxylate or nonylphenol ethoxylate.
- nonylphenols and their ethoxylated derivatives are known to be toxic, specifically as endocrine-hormone disrupters. Thus, there is a need to replace these chemistries with nonylphenol-free alternatives that are more environmentally friendly.
- LAEs linear/branched alcohol ethoxylates
- a polymer composition includes a water-in-oil emulsion containing an aqueous phase including water and a water-soluble or water-dispersible polymer, and an oil phase including an oil and an emulsifying agent; and an inversion surfactant having the structure of Formula 1: wherein R 3 , R 5 , R 9 , and R 10 are independently hydrogen or C 1- C 22 alkyl; R 4 is C 4 -C 30 alkyl; R 6 is H, alkyl, or aryl; R 11 is hydrogen, alkyl, alkylaryl, or aryl; X is -O- or -NR 8 ; R 8 is hydrogen or C 1 -C 4 alkyl; and n is an integer from 1 to 20.
- a polymer composition includes a water-in-oil emulsion including an aqueous phase containing water and a water-soluble or water-dispersible polymer, an oil phase containing an oil and an emulsifying agent, and an inversion surfactant having the structure of Formula 1: wherein R 3 , R 5 , R 9 , and R 10 are independently hydrogen or C 1 -C 22 alkyl; R 4 is C 4 -C 30 alkyl; R 6 is H, alkyl, or aryl; R 11 is hydrogen, alkyl, alkylaryl, or aryl; X is -O- or -NR 8 ; R 8 is hydrogen or C 1 -C 4 alkyl; and n is an integer from 1 to 20.
- R 3 , R 5 , R 9 , and R 10 are independently hydrogen or C 1 -C 22 alkyl
- R 4 is C 4 -C 30 alkyl
- R 6 is H, alkyl, or aryl
- R 11 is hydrogen
- a polymer composition is further provided that includes a water-in-oil emulsion containing an aqueous phase including water and a water-soluble or water-dispersible polymer, and an oil phase containing an oil and an emulsifying agent; and an aqueous solution containing an inversion surfactant having the structure of Formula 1: wherein R 3 , R 5 , R 9 , and R 10 are independently hydrogen or C 1 -C 22 alkyl; R 4 is C 4 -C 30 alkyl; R 6 is H, alkyl, or aryl; R 11 is hydrogen, alkyl, alkylaryl, or aryl; X is -O- or -NR 8 ; R 8 is hydrogen or C 1 -C 4 alkyl; and n is an integer from 1 to 20.
- a polymer composition is also provided that comprises a water-soluble or water-dispersible polymer, an oil, a suspending agent, and a surfactant having the structure of Formula 1: wherein R 3 , R 5 , R 9 , and R 10 are independently hydrogen or C 1 -C 22 alkyl; R 4 is C 4 -C 30 alkyl; R 6 is H, alkyl, or aryl; X is -O- or -NR 8 ; R 8 is hydrogen or C 1 -C 4 alkyl; R 11 is hydrogen, alkyl, alkylaryl, or aryl; and n is an integer from 1 to 20.
- R 3 , R 5 , R 9 , and R 10 are independently hydrogen or C 1 -C 22 alkyl
- R 4 is C 4 -C 30 alkyl
- R 6 is H, alkyl, or aryl
- X is -O- or -NR 8
- R 8 is hydrogen or C 1 -C 4 alkyl
- X is -O-.
- n can be an integer from 2 to 20.
- n is an integer from 4 to 16. More preferably, n is an integer from 4 to 10.
- R 4 can be C 4 -C 16 alkyl; R 4 can also be C 4 -C 12 alkyl; preferably, R 4 is C 8 -C 12 alkyl; and more preferably, R 4 is octyl.
- R 3 , R 5 , R 9 , and R 10 can independently be hydrogen or methyl, and preferably, R 3 , R 5 , R 9 , and R 10 are hydrogen.
- R 6 can be hydrogen, methyl, butyl, or benzyl, or a combination thereof.
- R 6 can be methyl, hydrogen, or a combination thereof.
- R 6 can be hydrogen.
- R 11 can be hydrogen or alkyl; preferably, hydrogen or methyl; most preferably, hydrogen.
- the inversion surfactant having the structure of Formula 1 can have a concentration of from about 0.1 wt.% to about 10 wt.% based on the total weight of the polymer composition.
- the inversion surfactant having the structure of Formula 1 has a concentration of from about 0.5 wt.% to about 5 wt.% based on the total weight of the polymer composition.
- the polymer composition can comprise from about 5 wt.% to about 70 wt.%, of the water-soluble or water-dispersible polymer.
- the polymer composition comprises from about 18 wt.% to about 65 wt.% of the water-soluble or water-dispersible polymer.
- a method of dissolving the water-soluble or water-dispersible polymer of the polymer composition comprising contacting the water-in-oil emulsion with the inversion surfactant having the structure of Formula 1.
- a further method of dissolving the water-soluble or water-dispersible polymer of the polymer composition comprising contacting the water-in-oil emulsion further comprising the inversion surfactant having the structure of Formula 1 with an aqueous solution.
- Another method of dissolving the water-soluble or water-dispersible polymer of the polymer composition comprising contacting the water-in-oil emulsion with an aqueous solution comprising the inversion surfactant having the structure of Formula 1.
- the polymer composition or methods described herein can have the polymer composition further comprise an ethoxylated C 10 -C 16 alcohol; a C 12 -C 13 primary alcohol of linear and mono-methyl branched alcohol having on average 9 moles ethylene oxide; an ethoxylate of a saturated C 12-15 alcohol; an ethoxylated C 12-14 alcohol; an ethoxylated primary branched saturated C 13 alcohol; an ethoxylated C 10 Guerbet alcohol; an ethoxylated saturated iso-C 13 alcohol; a saturated, predominantly unbranched C 13-15 oxo alcohol having 11 ethylene oxide groups; a secondary alcohol ethoxylate; a nonionic, alkoxylated alcohol; a polyoxyethylene (9) synthetic primary C 13 /C 15 alcohol; an isotridecyl alcohol ethoxylated with an average of 9 moles ethylene oxide; an ethoxylated linear primary C 12-14 alcohol; an ethoxylated nonylphenol; tert-
- the methods described herein can have the inversion surfactant be activated by contacting the inversion surfactant with an inversion aid.
- the inversion aid can comprise glycol, , a polypropylene glycol, polyglycerol, urea, sorbitol, sucrose, glycerol, a polyglycerol, a phosphate, choline chlorine, guanidine, dioctyl-sulfosuccinate, malic acid, lactic acid, N-(phosphonomethyl)glycine, 2-phosphonopropanoic acid, 3-phosphonopropanoic acid, 4-phosphonobutanoic acid, a phosphinosuccinic oligomer, or a combination thereof.
- the inversion surfactant can be activated by contacting the inversion surfactant with an aqueous solution.
- the aqueous solution can contain a salt.
- the inversion surfactant can be activated by increasing the temperature of the aqueous solution, and preferably, the temperature of the aqueous solution is increased from about 10°C to about 65°C.
- a compound is also provided that has the structure of Formula 2: wherein R 3 , R 5 , R 9 , and R 10 are independently hydrogen or C 1 -C 22 alkyl; R 4 is C 4 -C 30 branched alkyl; R 6 is H, alkyl, or aryl; R 11 is hydrogen, alkyl, alkylaryl, or aryl; X is -O- or -NR 8 ; R 8 is hydrogen or C 1 -C 4 alkyl; and n is an integer from 1 to 20.
- the compound having the structure of formula 2 has R 3 , R 5 , R 9 , and R 10 are hydrogen; R 4 is C 8 -C 16 branched alkyl; R 6 and R 11 are hydrogen; X is -O-; and n is an integer from 1 to 20.
- Inversion surfactants are provided that can dissolve water-soluble or water-dispersible polymers rapidly and completely in aqueous solution.
- the polymer compositions containing the surfactants described herein can be used in various industries including for water clarification, papermaking, sewage and industrial water treatment, drilling mud stabilizers, and enhanced oil recovery.
- Polymer compositions including water-in-oil emulsions and inversion surfactants are provided. Also, methods of dissolving a water-soluble or water-dispersible polymer are disclosed.
- the polymer composition comprises a water-in-oil emulsion comprising an aqueous phase comprising water and a water-soluble or water-dispersible polymer, and an oil phase comprising an oil and an emulsifying agent; and an inversion surfactant having the structure of Formula 1: wherein R 3 , R 5 , R 9 , and R 10 are independently hydrogen or C 1 -C 22 alkyl; R 4 is C 4 -C 22 alkyl; R 6 is H, alkyl, or aryl; R 11 is hydrogen, alkyl, alkylaryl, or aryl; X is -O- or -NR 8 ; R 8 is hydrogen or C 1 -C 4 alkyl; and n is an integer from 1 to 20.
- a polymer composition is further provided that includes a water-in-oil emulsion containing an aqueous phase comprising water and a water-soluble or water-dispersible polymer, and an oil phase comprising an oil and an emulsifying agent; and an aqueous solution containing an inversion surfactant having the structure of Formula 1: wherein R 3 , R 5 , R 9 , and R 10 are independently hydrogen or C 1 -C 22 alkyl; R 4 is C 4 -C 30 alkyl; R 6 is H, alkyl, or aryl; R 11 is hydrogen, alkyl, alkylaryl, or aryl; X is -O- or -NR 8 ; R 8 is hydrogen or C 1 -C 4 alkyl; and n is an integer from 1 to 20.
- a polymer composition is also provided that comprises a water-soluble or water-dispersible polymer, an oil, a suspending agent, and a surfactant having the structure of Formula 1: wherein R 3 , R 5 , R 9 , and R 10 are independently hydrogen or C 1 -C 22 alkyl; R 4 is C 4 -C 30 alkyl; R 6 is H, alkyl, or aryl; X is -O- or -NR 8 ; R 8 is hydrogen or C 1 -C 4 alkyl; R 11 is hydrogen, alkyl, alkylaryl, or aryl; and n is an integer from 1 to 20.
- R 3 , R 5 , R 9 , and R 10 are independently hydrogen or C 1 -C 22 alkyl
- R 4 is C 4 -C 30 alkyl
- R 6 is H, alkyl, or aryl
- X is -O- or -NR 8
- R 8 is hydrogen or C 1 -C 4 alkyl
- a compound is also provided that has the structure of Formula 2: wherein R 3 , R 5 , R 9 , and R 10 are independently hydrogen or C 1 -C 22 alkyl; R 4 is C 4 -C 30 branched alkyl; R 6 is H, alkyl, or aryl; R 11 is hydrogen, alkyl, alkylaryl, or aryl; X is -O- or -NR 8 ; R 8 is hydrogen or C 1 -C 4 alkyl; and n is an integer from 1 to 20.
- the compound having the structure of formula 2 has R 3 , R 5 , R 9 , and R 10 are hydrogen; R 4 is C 8 -C 16 branched alkyl; R 6 and R 11 are hydrogen; X is -O-; and n is an integer from 1 to 20.
- X is -O-.
- n can be an integer from 2 to 20.
- n is an integer from 4 to 16. More preferably, n is an integer from 4 to 10.
- R 4 can be C 4 -C 16 alkyl; R 4 can also be C 4 -C 12 alkyl; preferably, R 4 is C 8 -C 12 alkyl; and more preferably, R 4 is octyl.
- R 3 , R 5 , R 9 , and R 10 can independently be hydrogen or methyl.
- R 3 , R 5 , R 9 , and R 10 are hydrogen.
- R 6 can be hydrogen, methyl, butyl, or benzyl.
- R 6 can be methyl.
- R 6 can be hydrogen.
- R 11 can be hydrogen or alkyl; preferably, hydrogen or methyl; most preferably, hydrogen.
- the polymer composition can comprise from about 5 wt.% to about 70 wt.%, from about 10 wt.% to about 70 wt.%, from about 20 wt.% to about 70 wt.%, from about 30 wt.% to about 70 wt.%, from about 40 wt.% to about 70 wt.%, from about 50 wt.% to about 70 wt.%, from about 60 wt.% to about 70 wt.%, from about 10 wt.% to about 60 wt.%, from about 10 wt.% to about 50 wt.%, from about 15 wt.% to about 70 wt.%, from about 15 wt.% to about 65 wt.%, from about 18 wt.% to about 65 wt.%, from about 20 wt.% to about 60 wt.%, from about 20 wt.% to about 50 wt.%, from about 25 wt.% to about
- the polymer composition can be a slurry comprising a water-soluble polymer suspended in an oil-based vehicle with a suspension agent and a surfactant of Formula 1 or 2.
- the approximate size of the water-soluble polymer is preferably 75-200 mesh.
- the oil-based vehicle can be petroleum distillate.
- Petroleum distillates are products distilled from petroleum crude oil and use different CAS # identifiers depending upon the molecular weight distribution and processing technology used.
- a petroleum distillate suitable for the present composition can be, for example, CAS #64742-47-8 .
- the suspension aid can be a variation of diblock copolymers based on styrene and ethylene/propylene.
- the composition can also contain a dispersant such as organophilic clay or a synthetic alternative as the suspension agent.
- the inversion surfactant having the structure of Formula 1 or 2 can be blended with another inversion surfactants.
- the other inversion surfactants of interest include those listed in the following table and combinations thereof.
- Trade Name Chemistry Alfonic 1412-7 Ethoxylated C 10 -C 16 alcohols Novel 23E9 C 12 -C 13 primary alcohol of linear and mono-methyl branched alcohols having on average 9 moles EO
- Synperonic A11 Ethoxylate of a saturated C 12-15 alcohol
- Surfonic 1412-12 Ethoxylated C 12-14 alcohol
- Synperonic 13/7 Ethoxylated primary branched saturated C 13 alcohol
- Lutensol TO10 Ethoxylated C 10 Guerbet alcohol Lutensol TO12 Ethoxylated saturated iso-C 13 alcohol Lutensol AO11 Saturated, predominantly unbranched C 13-15 oxo alcohols having 11 EO groups Tergitol 15-S-9 Secondary Alcohol Ethoxylate Tergitol 15-S-12 Secondary Alcohol Ethoxylate Plurafac
- the inversion surfactant having the structure of Formula 1 or 2 can be blended with an ethoxylated C 10 -C 16 alcohol; a C 12 -C 13 primary alcohol of linear and mono-methyl branched alcohol having on average 9 moles ethylene oxide; an ethoxylate of a saturated C 12-15 alcohol; an ethoxylated C 12-14 alcohol; an ethoxylated primary branched saturated C 13 alcohol; an ethoxylated C 10 Guerbet alcohol; an ethoxylated saturated iso-C 13 alcohol; a saturated, predominantly unbranched C 13-15 oxo alcohol having 11 ethylene oxide groups; a secondary alcohol ethoxylate; a nonionic, alkoxylated alcohol; a polyoxyethylene (9) synthetic primary C 13 /C 15 alcohol; an isotridecyl alcohol ethoxylated with an average of 9 moles ethylene oxide; an ethoxylated linear primary C 12-14 alcohol; an ethoxylated nonylphenol; tert
- inversion surfactant is activated by contacting the inversion surfactant with an inversion aid.
- the inversion aid comprises glycol, a polyethylene glycol, a polypropylene glycol, polyglycerol, urea, sorbitol, sucrose, glycerol, a phosphate, choline chlorine, guanidine, dioctyl-sulfosuccinate, malic acid, lactic acid, N-(phosphonomethyl)glycine, 2-phosphonopropanoic acid, 3-phosphonopropanoic acid, 4-phosphonobutanoic acid, a phosphinosuccinic oligomer or a combination thereof.
- the inversion surfactant having the structure of Formula 1 can be prepared by the following synthetic scheme: wherein X, R 3 , R 4 , R 5 , R 6 , R 9 , R 10 , and R 11 are defined as for Formula 1.
- the inversion surfactant having the structure of Formula 1 can have a concentration of from about 0.1 wt.% to about 10 wt.% based on the total weight of the polymer composition.
- the inversion surfactant having the structure of Formula 1 has a concentration of from about 0.5 wt.% to about 5 wt.% based on the total weight of the polymer composition.
- the water-in-oil polymer emulsion can further comprise an emulsifying agent.
- the surfactant or blend of surfactants can have a low hydrophile-lipophile balance (HLB) to aid preparation of an oil-continuous emulsion.
- HLB hydrophile-lipophile balance
- Appropriate surfactants for water-in-oil emulsion polymerizations which are commercially available are compiled in the North American Edition of McCutcheon's Emulsifiers & Detergents.
- the emulsifying agent can comprise nonionic ethoxylated fatty acid esters, ethoxylated sorbitan fatty acid esters, sorbitan esters of fatty acids such as sorbitan monolaurate, sorbitan monostearate, and sorbitan monooleate, block copolymers of ethylene oxide and hydroxyacids having a C 10 -C 30 linear or branched hydrocarbon chain, linear or branched alcohol alkoxylates, or a combination thereof.
- the emulsifying agent can be a single nonionic surfactant or blend thereof having a combined HLB value of about 2 to 10, for example about 3 to 10, or about 4 to 10, or about 5 to 10, or about 6 to 10, or about 7 to 10, or about 8 to 10, or about 2 to 9, or about 2 to 8, or about 2 to 7, or about 2 to 6, or about 2 to 5, or about 3 to 9, or about 4 to 8.
- the water-in-oil emulsion can also comprise an alcohol alkoxylate.
- the alcohol alkoxylate can comprise a linear or branched alcohol ethoxylate, or a combination thereof.
- the surfactant compositions are useful as inverters (activators) of water-in-oil (inverse) emulsion polymers in various industries including for water clarification, papermaking, sewage and industrial water treatment, drilling mud stabilizers, and enhanced oil recovery.
- the water-soluble or water-dispersible polymers useful in the polymer compositions include various polymers and their mixtures, or derivatives.
- the water-soluble or water-dispersible polymers used can be an anionic, a cationic, a nonionic, a zwitterionic, or an amphoteric polymer.
- the water-soluble or water-dispersible polymers contained in the polymer compositions can comprise polyacrylamides, polyacrylates, copolymers thereof, and hydrophobically modified derivatives of these polymers.
- the water-soluble or water-dispersible polymers used in the polymer compositions described herein can include the water-soluble or water-dispersible polymers described in U.S. Patent Nos. 3,624,019 and 3,734,873 ; the water-soluble or water-dispersible polymers can have various architectures as disclosed in EP 202780 (linear and cross-linked), and EP 374458 , U.S. Patent Nos. 5,945,494 and 5,961,840 (branched) . Additionally, the water-soluble or water-dispersible polymers can contain hydrophobic monomers as disclosed in U.S. Patent No. 4,918,123 .
- the polymers usefully incorporated in the polymer compositions typically have a weight average molecular weight (Mw) of about 500,000 Daltons to about 100,000,000 Daltons, or about 1,000,000 Daltons to about 50,000,000 Daltons, or about 5,000,000 Daltons to about 30,000,000 Daltons.
- Mw weight average molecular weight
- the water-soluble or water-dispersible polymer can comprise about 1 mol% to about 100 mol% acrylamide monomers, or about 1 mol % to about 90 mol %, or about 1 mol % to about 80 mol %, or about 1 mol % to about 70 mol %, or about 1 mol % to about 60 mol %, or about 1 mol % to about 50 mol %, or about 1 mol % to about 40 mol %, or about 1 mol % to about 30 mol %, or about 1 mol % to about 20 mol %, or about 1 mol % to about 10 mol %, or about 10 mol % to about 100 mol %, or about 20 mol % to about 100 mol %, or about 30 mol % to about 100 mol %, or about 40 mol % to about 100 mol %, or about 50 mol % to about 100 mol %, or about 60 mol % to about 100 mol
- the water-soluble polymer or water-dispersible polymer can be present within the water-in-oil emulsion at about 15 wt % to 70 wt%, or about 17 wt % to 70 wt %, or about 19 wt % to 70 wt%, or about 21 wt% to 70 wt%, or about 23 wt % to 70 wt %, or about 25 wt % to 70 wt %, or about 15 wt % to 68 wt%, or about 15 wt% to 66 wt%, or about 15 wt % to 64 wt%, or about 15 wt% to 62 wt%, or about 15 wt % to 60 wt%, or about 15 wt% to 58 wt%, or about 15 wt % to 56 wt%, or about 25 wt% to 65 wt%, or about 30 wt % to 60 wt
- Inverse emulsion polymers are prepared by dissolving the required monomers in the water phase, dissolving the emulsifying agent in the oil phase, emulsifying the water phase in the oil phase to prepare a water-in-oil emulsion, homogenizing the water-in-oil emulsion and polymerizing the monomers to obtain the polymer.
- a self-inverting surfactant may be added to the water-soluble polymer dispersed within the hydrocarbon matrix to obtain a self-inverting water-in-oil emulsion.
- a polymer solution can be made-up by inverting the polymer dispersed in oil in to water containing the surfactant.
- Water is present in the water-in-oil emulsion at about 3 wt % to 50 wt %, or about 5 wt% to 50 wt%, or about 10 wt% to 50 wt%, or about 15 wt% to 50 wt%, or about 20 wt % to 50 wt %, or about 25 wt % to 50 wt %, or about 3 wt % to 35 wt %, or about 3 wt % to 30 wt %, or about 3 wt % to 25 wt %, or about 5 wt % to 45 wt %, or about 5 wt % to 40 wt %, or about 5 wt % to 35 wt %, based on the total weight of the water-in-
- the water-in-oil emulsion also contains an amount of oil sufficient to form an oil phase within the water-in-oil emulsion.
- the oil in the oil phase can be a mixture of compounds, wherein the mixture is less than 0.1 wt % soluble in water at 25° C and is a liquid over the range of 20° C to 90° C.
- the oil in the oil phase can comprise a linear, branched, or cyclic hydrocarbon moieties, aryl or alkaryl moieties, or combinations thereof.
- the oil in the oil phase can have a density of about 0.8 g/L to 1.0 g/L, for example about 0.8 g/L to 0.9 g/L.
- oils for the oil phase can include a petroleum distillate, decane, dodecane, isotridecane, cyclohexane, toluene, xylene, and mixed paraffin solvents such as those sold under the trade name ISOPAR ® by ExxonMobil Corp. of Irving, Texas.
- the oil phase is present in the water-in-oil emulsion at about 10 wt% to 40 wt %, or about 15 wt % to 40 wt %, or about 20 wt % to 40 wt %, or about 22 wt % to 40 wt %, or about 24 wt % to 40 wt %, or about 26 wt % to 40 wt %, or about 28 wt % to 40 wt %, or about 30 wt % to 40 wt %, or about 10 wt % to 38 wt %, or about 10 wt% to 36 wt%, or about 10 wt% to 34 wt%, or about 10 wt% to 32 wt%, or about 10 wt% to 30 wt%, or about 10 wt% to 25 wt%, or about 10 wt% to 20 wt%, or about 15 wt % to 35
- the inversion surfactant of Formula I aids the inversion of the water-in-oil emulsion compared to a water-in-oil emulsion comprising no inversion surfactant or compared to a water-in-oil emulsion comprising a comparator inversion surfactant.
- the inversion surfactant of Formula I, of the present disclosure increase the speed and/or percent completion of the inversion process compared to a water-in-oil emulsion comprising no inversion surfactant or compared to a water-in-oil emulsion comprising a comparator inversion surfactant.
- the inversion surfactant is added to the emulsion at about 0.1 wt% to 20.0 wt% based on the total weight of the emulsion, or about 0.1 wt% to 15.0 wt%, or about 0.1 wt% to 10.0 wt%, or about 0.1 wt% to 7.5 wt%, or about 0.1 wt % to 5.0 wt%, or about 0.5 wt% to 4.5 wt%, or about 1.0 wt% to 4.0 wt%, or about 1.5 wt% to 3.5 wt%, or about 2.0 wt% to 3.0 wt%, or about 0.1 wt% to 4.5 wt%, or about 0.1 wt% to 4.0 wt%, or about 0.1 wt% to 3.5 wt%, or about 0.1 wt% to 3.0 wt%, or about 0.5
- the inversion surfactant can be added to the aqueous solution contacted with the emulsion to activate the polymer in a concentration of about 0.1 wt% to 20.0 wt% based on the total weight of the aqueous solution, or about 0.1 wt% to 15.0 wt%, or about 0.1 wt% to 10.0 wt%, or about 0.1 wt% to 7.5 wt%, or about 0.1 wt % to 5.0 wt%, or about 0.5 wt% to 4.5 wt%, or about 1.0 wt% to 4.0 wt%, or about 1.5 wt% to 3.5 wt%, or about 2.0 wt% to 3.0 wt%, or about 0.1 wt% to 4.5 wt%, or about 0.1 wt% to 4.0 wt%, or about 0.1 wt% to 3.5 wt%, or about 0.1 wt% to 3.0 wt%, or
- the effective amount of the polymer composition can be from about 1 ppm to about 10000 ppm, from about 1 ppm to about 9000 ppm, from about 1 ppm to about 8000 ppm, from about 1 ppm to about 7000 ppm, from about 1 ppm to about 6000 ppm, from about 1 ppm to about 5000 ppm, from about 1 ppm to about 4000 ppm, from about 1 ppm to about 3000 ppm, from about 1 ppm to about 2000 ppm, from about 1 ppm to about 1000 ppm, based on the total weight of the process fluid.
- the effective amount of the polymer composition is from about 1 ppm to about 900 ppm, from about 1 ppm, to about 800 ppm, from about 1 ppm to about 700 ppm, from about 1 ppm to about 600 ppm, or from about 1 ppm to about 500 ppm.
- the effective amount of the polymer composition can be from about 1 ppm to about 250 ppm, from about 1 ppm to about 200 ppm, from about 1 ppm to about 100 ppm, from about 1 ppm to about 75 ppm, from about 1 ppm to about 50 ppm, from about 1 ppm to about 25 ppm, from about 1 ppm to about 15 ppm, or from about 1 ppm to about 10 ppm, based on the total weight of the process fluid.
- the inversion and dilution to a target concentration of less than 1 wt % can be accomplished in about 1 to 15 minutes, for example about 1 to 14, 1 to 13, 1 to 12, 1 to 11, 1 to 10, 1 to 9, 1 to 8, 1 to 7, 1 to 6, 1 to 5, 2 to 15, 3 to 15, 4 to 15, 5 to 15, 6 to 15, 7 to 15, 8 to 15, 9 to 15, 10 to 15, 2 to 10, 2 to 9, 2 to 8, 2 to 7, 2 to 6, or 2 to 5 minutes.
- the aqueous solutions can comprise about 100 ppm to 10,000 ppm (0.01 wt% to 1.00 wt%) water-soluble or water-dispersible polymer, or about 200 ppm to 5000 ppm, or about 200 ppm to 4000 ppm, or about 200 ppm to 3000 ppm, or about 200 ppm to 2500 ppm water-soluble or water-dispersible polymer, based on the total weight of the aqueous solution.
- polymer means a water-soluble or water-dispersible polymer.
- polymer encompasses and includes homopolymers, copolymers, terpolymers and polymers with more than three monomers, crosslinked or partially crosslinked polymers, and combinations or blends of these.
- polymer solution or “polymer dispersion” means a polymer composition substantially dispersed or dissolved in water, a water source, or a water-based solution.
- Water-based solutions include one or more dissolved salts, buffers, acids, bases, surfactants, or other dissolved, dispersed, or emulsified compounds, materials, components, or combinations thereof.
- inverse emulsion polymer and "inverse latex polymer” mean a water-in-oil polymer emulsion comprising a water-soluble polymer (which could be cationic, anionic, nonionic, amphoteric polymer, or zwitterionic) according to this invention in the aqueous phase, a hydrocarbon oil for the oil phase and a water-in-oil emulsifying agent.
- Inverse emulsion polymers are hydrocarbon continuous with the water-soluble polymers dispersed within the hydrocarbon matrix. The inverse emulsion polymers are then "inverted” or activated for use by releasing the polymer from the particles using shear, dilution, and generally another surfactant. See U.S. Pat. No. 3,734,873 .
- water source means a source of water comprising, consisting essentially of, or consisting of fresh water, deionized water, distilled water, produced water, municipal water, waste water such as runoff water or municipal waste water, treated or partially treated waste water, well water, brackish water, "gray water", sea water, or a combination of two or more such water sources as determined by context.
- a water source can include one or more salts, ions, buffers, acids, bases, surfactants, or other dissolved, dispersed, or emulsified compounds, materials, components, or combinations thereof.
- water-in-oil emulsion mean a discontinuous internal water phase within a continuous oil phase, wherein the water phase includes at least one monomer or polymer. In general and as determined by context, these terms denote an emulsion prior to addition of inversion surfactants.
- oil or “hydrocarbon solvent” as applied to an oil phase of a water-in-oil emulsion, means any compound or blend thereof that is less than 0.1 wt % soluble in water at 25° C., is substantially chemically inert within a water-in-oil emulsion as described herein, and is a liquid over at least the range of 20° C. to 100° C.
- water phase means a water source having at least a monomer or polymer dispersed or dissolved therein, further wherein the dispersion or solution is a discontinuous phase within a water-in-oil emulsion.
- an alkyl group as described herein alone or as part of another group is an optionally substituted linear saturated monovalent hydrocarbon substituent containing from one to sixty carbon atoms and preferably one to thirty carbon atoms in the main chain or eight to thirty carbon atoms in the main chain, or an optionally substituted branched saturated monovalent hydrocarbon substituent containing three to sixty carbon atoms, and preferably eight to thirty carbon atoms in the main chain.
- unsubstituted alkyl groups include methyl, ethyl, n -propyl, i -propyl, n -butyl, i -butyl, s -butyl, t -butyl, n -pentyl, i -pentyl, s -pentyl, t -pentyl, and the like.
- aryl or “ar” as used herein alone or as part of another group denote optionally substituted homocyclic aromatic groups, preferably monocyclic or bicyclic groups containing form 6 to 12 carbon atoms in the ring portion, such as phenyl, biphenyl, naphthyl, substituted phenyl, substituted biphenyl, or substituted naphthyl. Phenyl and substituted phenyl are the more preferred aryl groups.
- aryl also includes heteroaryl functional groups.
- Arylalkyl means an aryl group attached to the parent molecule through an alkylene group.
- the number of carbon atoms in the aryl group and the alkylene group is selected such that there is a total of about 6 to about 18 carbon atoms in the arylalkyl group.
- a preferred arylalkyl group is benzyl.
- substituted means that in the group in question (i.e., the alkyl, aryl, or other group that follows the term), at least one hydrogen atom bound to a carbon atom is replaced with one or more substituent groups such as hydroxy (-OH), alkylthio, amido (-CON(R A )(R B ), wherein R A and R B are wherein R A and R B are independently hydrogen, alkyl, or aryl), amino (-N(R A )(R B ), wherein R A and R B are independently hydrogen, alkyl, or aryl), halo (fluoro, chloro, bromo, or iodo), silyl, nitro (-NO 2 ), an ether (-OR A wherein R A is alkyl or aryl), an ester (-OC(O)R A wherein R A is alkyl or aryl
- substituted introduces a list of possible substituted groups, it is intended that the term apply to every member of that group. That is, the phrase “optionally substituted alkyl or aryl” is to be interpreted as “optionally substituted alkyl or optionally substituted aryl.”
- heterocyclo refers to a monocyclic, bicyclic, or tricyclic group containing 1 to 4 heteroatoms selected from N, O, S(O) n , P(O) n , PR z , NH or NR z , wherein R z is a suitable substituent.
- Heterocyclic groups optionally contain one or two double bonds.
- Heterocyclic groups include, but are not limited to, azetidinyl, tetrahydrofuranyl, imidazolidinyl, pyrrolidinyl, piperidinyl, piperazinyl, oxazolidinyl, thiazolidinyl, pyrazolidinyl, thiomorpholinyl, tetrahydrothiazinyl, tetrahydro-thiadiazinyl, morpholinyl, oxetanyl, tetrahydrodiazinyl, oxazinyl, oxathiazinyl, indolinyl, isoindolinyl, quinuclidinyl, chromanyl, isochromanyl, and benzoxazinyl.
- Examples of monocyclic saturated or partially saturated ring systems are tetrahydrofuran-2 yl, tetrahydrofuran-3-yl, imidazolidin-1-yl, imidazolidin-2 yl, imidazolidin-4-yl, pyrrolidin-1-yl, pyrrolidin-2 yl, pyrrolidin-3-yl, piperidin-1-yl, piperidin-2 yl, piperidin-3-yl, piperazin-1-yl, piperazin-2 yl, piperazin-3-yl, 1,3-oxazolidin-3-yl, isothiazolidine, 1,3-thiazolidin-3-yl, 1,2 pyrazolidin-2 yl, 1,3-pyrazolidin-1-yl, thiomorpholin-yl, 1,2 tetrahydrothiazin-2 yl, 1,3-tetrahydrothiazin-3-yl, tetrahydrothiadiazin-
- the reaction was subsequently cooled to room temperature and acidified to a pH of 2.0 with concentrated hydrochloric acid. Approximately 300 mL deionized (DI) water was added and the reaction mixture was stirred for 15 minutes. The reaction mixture was extracted twice with 20 mL dichloromethane. The combined organic phase was then washed three times with 200 mL DI water, dried over Na 2 SO 4 , and concentrated in vacuo to provide off-white solids. The crude solids were washed with minimum amounts of cold hexanes to provide pure 4-(octyloxy)phenol. The sample was dried in a 40°C oven.
- DI deionized
- the flask When the sample contained less than 0.1% water, the flask was cooled to 60°C. Once the reaction mixture reached 60°C, the N 2 purge was increased. Under N 2 purge, the contents of the flask were poured into a tared nitrogen-filled one quart bottle. The contents of the bottle were then transferred to the Lab Oxyalkylation Unit Paar Reactor. The Paar Reactor was buttoned up and purged with nitrogen from three to four times. The pressure was set to 0.34 bar (5 psi) with nitrogen.
- the reactor was heated to 150 °C. Once stabilized, ethylene oxide was added until the pressure reached 4.13 bar (60 psi). The weight of the ethylene oxide added to the reactor was recorded. The pressure was allowed to decrease, indicating a chemical reaction. When the pressure reached 0.69 bar (10 psi), the desired amount of ethylene oxide needed to complete a one-mole addition was added, or until the pressure reached 4.13 bar (60 psi). The pressure was continually allowed to decrease and ethylene oxide added until the pressure reached 4.13 bar (60 psi) until the desired amount of ethylene oxide was added and reacted.
- the rate of inversion in the following examples was measured using a qualitative analytical tool referred to as a "torque monitor.” It consisted of a DC stir motor, a controller that can report the torque (DC voltage) required to maintain a constant stir speed, and a computer to record the torque reading as a function of time.
- the percent inversion at 2 minute and 5 minute was estimated from 2 and 5 minute torque readings compared to the final torque readings.
- activating surfactants used are listed in Table 2. Table 2. Activating surfactants used in Example 4 Name Component 4OP-10eo 4-octyloxyphenol ethoxylate (9.9 ethylene oxide units) Activator #1 DOW TERGITOL NP-9.5 Activator #2 SASOL ALFONIC 1412-7 Activator #3 HUNTSMAN SURFONIC TDA-9
- a 50 mole% cationic polymer without activating surfactant was synthesized as follows.
- Monomer (aqueous) phase make-up Into a 1-L beaker was added 227.7 g of a 49.5% aqueous acrylamide solution, 7.5 g adipic acid, 0.1 g sodium formate, and 52.5 g deionized water. The resulting components were stirred. To the resulting solution was added 0.13 g Versene 220 (tetrasodium ethylenediaminetetraacetate tetrahydrate available from Dow Chemical Company) and 384.1 g 80% DMAEA.MCQ (dimethylaminoethylacrylate methyl chloride quaternary salt) solution. The resulting mixture was stirred to produce a clear solution.
- Versene 220 tetrasodium ethylenediaminetetraacetate tetrahydrate available from Dow Chemical Company
- 384.1 g 80% DMAEA.MCQ dimethylaminoethylacrylate methyl chloride quaternary salt
- Oil phase preparation Into a 2 L beaker was added 11.1 g sorbitan monooleate, 15.9 g SURFONIC L24-5 (a linear alcohol ethoxylate), and 270.0 g ISOPAR-M (a low odor, low aromatic hydrocarbon solvent of normal alkanes, isoalkanes, and cycloalkanes).
- Emulsion make-up The oil phase components were mixed with an IKA ULTRA TURAX T-25 (fine head) homogenizer at 11,000 rpm for about one minute resulting in a homogenous surfactant solution. While stirring at 11,000 rpm, the monomer phase was added to the beaker over a 30-second period. The resulting emulsion was homogenized for an additional 85 seconds. The final emulsion (297 cP, #2 spindle-30 rpm) was charged into a 2 L reactor and cooled to 6.9°C.
- IKA ULTRA TURAX T-25 fine head homogenizer
- Polymerization was conducted under a nitrogen atmosphere. Initiation was accomplished by co-feeding 1.2 mL of a 1.2% sodium bromate solution at a rate between 0.79-2.78 mL/minute and 1 mL of a 0.58% sodium metabisulfite solution at a rate between 0.40-0.79 mL/minute in a manner that the temperature rise was about 1.5°C/min. At 34 min, the reaction temperature was 59.6°C, at which time the sodium bromate and sodium metabisulfite solution feed rates were held at 1.59 mL/minute and the reaction temperature controlled at 59.6°C.
- the reaction mixture was cooled to room temperature yielding emulsion polymer 1 with a viscosity of 403 cP (#2 spindle/30 rpm), a median particle diameter size of 0.56 ⁇ m, and an RSV of 19.8 dL/g.
- Polymer 1 blends with activating surfactants 1, 2, and 4OP-1 0eo were made in the following manner. Approximately 0.3 g of activating surfactant was added into a tared 1-oz. bottle containing a 2.54 cm (1") magnetic stirring bar. Un-activated emulsion polymer 1 (i.e., emulsion polymer without an activating surfactant) was weighed into the bottle such that an activated polymer with 1% activator was obtained. Exact weights are shown in Table 3. The resulting mixture was stirred for one hour and then allowed to equilibrate for at least two additional hours.
- Polymer 1 blends with approximately 1.2% activator were obtained by adding the required amount of activator to polymer 1 blends containing approximately 1% activator. Polymer 1 blends with 1.4% activator were obtained similarly from the polymer 1 activator blends containing 1.2% activator (Table 5). With each successive addition of activating surfactant, the resulting mixture was stirred for one hour and allowed to equilibrate for at least an additional two hours. Table 3. Polymer 1 blends with activating surfactants at approximately 1% Activator Weight Activator (g) Weight Emulsion 1 (g) Wt.
- Polymer 1 blends with activating surfactants at approximately 1.2% Activator Wt. Remaining approximately 1% Polymer (g) Weight. Activator (g) Wt. Additional Activator (g) Wt. Percent Activator (%) 4OP-10eo 25.7620 0.2669 0.0468 1.216 Activator #1 25.5478 0.2627 0.0484 1.215 Activator #2 25.5864 0.2623 0.0475 1.209 Table 5.
- Polymer 1 blends with activating surfactants at approximately 1.4% Activator Wt.
- Figure 1 depicts the inversion torque profile (0.5% invert) for polymer 1 with approximately 1% activating surfactant.
- the rate of inversion for polymer 1 with 4OP-10eo is faster than for polymer 1 with either activator 1 or 2.
- Figure 2 depicts the inversion torque profile (0.5% invert) for polymer 1 with approximately 1.2% activating surfactant.
- the rate of inversion for polymer 1 with 4OP-10eo is faster than for polymer 1 with either activator 1 or 2.
- Figure 3 depicts the inversion torque profile (0.5% invert) for polymer 1 with approximately 1.4% activating surfactant.
- the rate of inversion for polymer 1 with 4OP-10eo and activator 1 are similar, but faster than for polymer 1 with activator 2.
- Figure 4 shows a comparison of the 2 minute percent inversion of polymer 1 with the activating surfactants.
- the percent inversion line is an average of two measurements (circles). The rate of inversion is faster for polymer 1 with 4OP-1 0eo than for polymer 1 with either activator 1 or 2 at equivalent activator concentrations.
- Figure 5 shows a comparison of the 5 minute percent inversion of polymer 1 with the activating surfactants.
- the percent inversion line is an average of two measurements (circles). The rate of inversion is faster for polymer 1 with 4OP-10eo than for polymer 1 with either activator 1 or 2 at equivalent activator concentrations. Full inversion is observed for polymer 1 formulated with 1.2% 4OP-10eo at 5 minutes.
- Emulsion polymer 2 was weighed into a 118.3 ml (4 oz.) bottle.
- Polymer 2 activator blends with approximately 2%, approximately 2.5%, and approximately 3% activator were made by blending activator into the emulsion while stirring. The resulting blends were stirred for one hour and allowed to stand for at least two hours before testing.
- Table 6 Polymer 2 blends with activating surfactants at approximately 2% Activator Weight Emulsion 1 (g) Weight Activator (g) Wt. Percent Activator (%) 4OP-10eo 70.36 1.47 2.05 Activator #1 77.82 1.62 2.04 Activator #3 70.04 1.45 2.03 Table 7.
- Polymer 2 blends with activating surfactants at approximately 2.5% Activator Weight Emulsion 1 (g) Weight Activator (g) Wt. Percent Activator (%) 4OP-10eo 70.37 1.82 2.52 Activator #1 71.78 1.82 2.47 Activator #3 67.10 1.72 2.50 Table 8. Polymer 2 blends with activating surfactants at approximately 3% Activator Weight Emulsion 1 (g) Weight Activator (g) Wt. Percent Activator (%) 4OP-10eo 97.02 3.03 3.03 Activator #1 97.01 3.14 3.14 Activator #3 97.01 3.02 3.02
- Figure 6 depicts the inversion torque profile (2% invert in DI water) for polymer 2 with approximately 2% activating surfactant.
- the rate of inversion for polymer 2 with activator 1 is faster than for polymer 2 with 4OP-1 0eo. Both are faster than polymer 2 activated with activators 2 and 3.
- Figure 7 depicts the inversion torque profile (2% invert in DI water) for polymer 2 with approximately 2.5% activating surfactant.
- the inversion rates for polymer 2 activated with activator 1 and 4OP-10eo are similar. Both are faster than polymer 2 activated with activators 2 and 3.
- Figure 8 depicts the inversion torque profile (2% invert in DI water) for polymer 2 with approximately 3% activating surfactant.
- the inversion rate for polymer 2 with activator 1 has the fastest rate of inversion.
- the rates of inversion for polymer 2 with activators 3 and 4OP-10eo are similar. All activated polymers invert faster than polymer 2 with activator 2.
- Figure 9 shows a comparison of the 2 minute percent inversion of polymer 2 with activating surfactants.
- the 2 minute percent inversion for polymer 2 with activator 1 is greater than for the other polymers.
- the 2 minute percent inversion for polymer 2 with 4OP-10eo is greater than for polymer 2 with activator 3 at 2, 2.5% activator concentration, but similar with 3% activator.
- Figure 10 shows a comparison of the 5 minute percent inversion of polymer 2 with activating surfactants.
- the 5 minute percent inversion for polymer 2 with activator 1 is greater than for the other polymers.
- the 5 minute percent inversion for polymer 2 with 4OP-10eo is greater than for polymer 2 with activator 3.
- Un-activated polyacrylamide emulsion polymer (emulsion polymer 3) without activating surfactant was used in this example.
- Polymer 3 blends with approximately 1.8% activator were obtained by adding the required amount of activator to polymer 3 blends containing approximately 1.5 % activator (Table 9). Polymer 3 blends with 2.1 and 2.4 % activator were obtained similarly from the polymer 3 activator blends containing 1.8% activator (Tables 11 and 12). With each successive addition of activating surfactant, the resulting mixture was stirred for an hour and allowed to equilibrate for at least an additional two hours. Table 9. Polymer 3 blends with activating surfactants at approximately 1.5% Activator Weight Emulsion 1 (g) Weight Activator (g) Wt.
- Polymer 3 blends with activating surfactants at approximately 2.1% Activator Wt. Remaining approximately 1% Polymer (g) Weight. Activator (g) Wt. Additional Activator (g) Wt. Percent Activator (%) 4OP-10eo 62.28 1.13 0.19 2.12 Activator #1 64.04 1.17 0.18 2.10 Activator #2 72.65 1.32 0.21 2.10 Activator #3 63.86 1.16 0.19 2.12 Table 12. Polymer 3 blends with activating surfactants at approximately 2.4% Activator Wt. Remaining approximately 1% Polymer (g) Weight. Activator (g) Wt. Additional Activator (g) Wt. Percent Activator (%) 4OP-10eo 43.16 0.91 0.13 2.42 Activator #1 43.89 0.92 0.12 2.37 Activator #2 54.23 1.13 0.18 2.42 Activator #3 45.31 0.96 0.13 2.40
- Figure 11 depicts the inversion torque profile (2% invert) for polymer 3 with approximately 1.5% activating surfactant.
- Polymer 3 with activator 1 outperforms activator 3, which outperforms 4OP-10eo, which outperforms activator 2.
- Figure 12 depicts the inversion torque profile (2% invert) for polymer 3 with approximately 1.8% activating surfactant.
- Polymer 3 with activator 1 performs similarly to activator 3, which outperforms 4OP-10eo, which outperforms activator 2.
- Figure 13 depicts the inversion torque profile (2% invert) for polymer 3 with approximately 2.1% activating surfactant.
- Polymer 3 with activator 1 outperforms 4OP-10eo, which outperforms activator 3, which outperforms activator 2.
- Figure 14 depicts the inversion torque profile (2% invert) for polymer 3 with approximately 2.4% activating surfactant.
- Polymer 3 with activator 1 outperforms 4OP-10eo, which outperforms activator 3, which outperforms activator 2.
- Figure 15 shows a comparison of the 2 minute percent inversion of polymer 3 with activating surfactants.
- the 2 minute percent inversion for polymer 3 with activator 1 is greater than for the other polymers.
- the 2 minute percent inversion for polymer 3 with 4OP-10eo is greater than for polymer 2 with activators 2 and 3.
- Figure 16 shows a comparison of the 5 minute percent inversion of polymer 3 with activating surfactants.
- the 5 minute percent inversion for polymer 3 with activator 1 is greater than for the other polymers.
- the 5 minute percent inversion for polymer 3 with 4OP-10eo is less than for polymer 3 with activator 3 at 1.5 and 1.8% activating surfactant.
- the relative 5 minute percent inversion crosses, and at 2.1 and 2.4% activator polymer 3 with 4OP-1 0eo is greater than for polymer 3 with activator 3.
- Polymer 1 was synthesized using a combination of sorbitan monooleate and a linear alcohol ethoxylate (7 eo) required 1.4% Activator #3 to meet an inversion of greater than 90%. Unexpectedly for Polymer 1, the Polymer 1 blend with 4OP-1 0eo inverted better than the blends with the DOW TERGITOL NP-9.5 or the standard linear alcohol ethoxylate (Activator #2). At 5 minutes, full inversion was observed for Polymer 1 with 1.2% 4OP-1 0eo ( Figure 5 ).
- Polymer 2 was formulated with 2.7% Activator #2 to meet an inversion of greater than 90%. With 2.5% activating surfactant, the rate of inversion of Polymer 2 with 4OP-1 0eo approached that of Polymer 2 with TERGITOL NP-9.5 ( Figure 7 ). Both of these activated polymers inverted better than Polymer 2 with the linear alcohol ethoxylates (Activators 2 and 3).
- Polymer 3 was formulated with 2.35% Activator #2 to meet an inversion of greater than 90%. As observed for Polymer 2, with 2.4% activating surfactant, the rate of inversion of Polymer 3 with 4OP-10eo approached that of Polymer 3 with Tergitol NP-9.5 ( Figure 14 ). Both of these activated polymers inverted better than Polymer 3 with the linear alcohol ethoxylates (Activators 2 and 3).
- Torque monitor tests were conducted at the 500 g scale in a 1000-mL beaker in different waters (tap water from the City of Naperville, IL; synthetic sea water; high TDS brine) at room temperature (approximately 22°C) at the concentrations indicated in the examples unless otherwise noted.
- the solution was stirred at 400 rpm with a 1 an HS-1 6.73 cm (2.65 inch) indicage stirrer positioned 1.27 cm (0.5 inch) from the bottom of the beaker and connected to the motor.
- Emulsion polymer was injected into the water vortex to start the experiment. Torque readings were collected every second and data worked-up in Microsoft Excel using a 20-period moving average.
- the percent inversion at 2 minute and 5 minute was estimated from 2 and 5 minute torque readings compared to the final torque readings.
- activating surfactants used are listed in Table 13. Table 13. Activating surfactants used in Example 4 Name Component 4OP-nEO 4-octyloxyphenol ethoxylate (where n indicates moles of EO units) Activator #1 DOW TERGITOL NP-9.5 Activator #2 SASOL ALFONIC 1412 7 Activator #3 HUNTSMAN SURFONIC TDA-9
- Example 4a 7:3 Acrylamide/Acrylic Acid Emulsion Polymer-Inversion in Tap Water
- Un-activated 7:3 acrylamide/acrylic acid emulsion co-polymer (emulsion polymer 4) without activating surfactant was used in this example.
- Emulsion polymer 4 was weighed into a 29.57 ml (4 oz.) bottle.
- Polymer 4 activator blends with approximately 1.35% activator were made by blending activator into the emulsion while stirring. The resulting blends were stirred for one hour and allowed to stand for at least two hours before testing.
- Table 14 Polymer 4 blends with activating surfactants at approximately 1.35% Activator Weight Emulsion 4 (g) Weight Activator(g) Wt.
- Figure 17 depicts the inversion torque profile (0.5% invert in tap water) for polymer 4 with approximately 1.35% activating surfactant.
- the inversion rates for polymer 4 activated with activator 1 and 4OP-7.2EO are similar.
- Polymer 4 blends with all 4OP-nEO activators are faster than polymer 4 activated with activators 2 and 3.
- Figure 18 shows a comparison of the 2 minute percent inversion of polymer 4 with activating surfactants.
- the 2 minute percent inversion for polymer 4 with 4OP-7.2EO was greater than for the other polymers.
- Figure 19 shows a comparison of the 5 minute percent inversion of polymer 4 with activating surfactants.
- the 5 minute percent inversion for polymer 4 with 4OP-7.2EO was greater than for the other polymers.
- Un-activated 7:3 acrylamide/acrylic acid emulsion co-polymer (emulsion polymer 5) without activating surfactant was used in this example.
- Emulsion polymer 5 was weighed into a 118.3 ml (4 oz.) bottle.
- Polymer 4 activator blends with approximately 2.5% activator were made by blending activator into the emulsion while stirring. The resulting blends were stirred for one hour and allowed to stand for at least two hours before testing.
- Table 15 Polymer 5 blends with activating surfactants at approximately 1.35% Activator Weight Emulsion 5 (g) Weight Activator(g) Wt.
- Synthetic Sea Water The 3.5% synthetic seawater used in the present Example was prepared by blending the components of Table 16. SSW was filtered through a WHATMAN 1 filter by suction filtration to remove any particulate. Table 16. Ingredients of 3.5% SSW Reagent Amount (g) Sodium chloride (NaCl) 24.65 Calcium chloride CaCl2 ⁇ 2H2O 1.57 Magnesium chloride (MgCl2 ⁇ 6H2O) 11.39 Sodium bicarbonate (NaHCO 3 ) 0.01 Sodium sulfate (Na2SO4) 4.38 Deionized water 957.99
- Figure 20 depicts the inversion torque profile (1% invert in SSW) for polymer 4 with approximately 2.5% activating surfactant.
- the rate of inversion for polymer 5 with activator 1 was faster than for other polymers.
- the rate of inversion for polymer 4 with activator 4OP-9EO was faster than polymer 5 with activator 2 and activator 3.
- Figure 21 shows a comparison of the 2 minute percent inversion of polymer 5 with activating surfactants.
- the 2 minute percent inversion for polymer 5 with activator 1 was greater than for the other polymers.
- Figure 22 shows a comparison of the 5 minute percent inversion of polymer 5 with activating surfactants.
- the 5 minute percent inversion for polymer 5 with activator 1 was greater than for the other polymers.
- Example 4c 7.5:2.5 Acrylamide/ATBS Emulsion Polymer-Inversion in SSW
- a 7.5:2.5 acrylamide/ATBS (acrylamido tertiary butyl sulfonic acid) emulsion co-polymer (emulsion polymer 6) without activating surfactant was used in this example.
- Emulsion polymer 6 was weighed into a 118.3 ml (4 oz.) bottle.
- Polymer 4 activator blends with approximately 2.5% activator were made by blending activator into the emulsion while stirring. The resulting blends were stirred for one hour and allowed to stand for at least two hours before testing.
- Table 17. Polymer 6 blends with activating surfactants at approximately 2% Activator Weight Emulsion 4 (g) Weight Activator(g) Wt.
- Figure 23 depicts the inversion torque profile (1% invert in SSW) for polymer 6 with approximately 2.0% activating surfactant.
- the rate of inversion for polymer 6 with activator 1, 4OP-8EO and 4OP-9EO are similar.
- Polymer 6 blends with all 4OP-nEO activators are faster than polymer 4 with activators 2 and 3.
- Polymer 5 blend with activator 2 failed the torque test.
- Figure 24 shows a comparison of the 2 minute percent inversion of polymer 6 with activating surfactants.
- the polymer 6 blends with 4OP-8EO, 4OP-9EO, and activator 1 invert fully in 2 minutes.
- Figure 25 shows a comparison of the 5 minute percent inversion of polymer 6 with activating surfactants.
- Plots of torque versus time provided a way to evaluate the speed at which inversion took place. Field applications generally required that inversion occurred rapidly.
- the slope of the torque versus time curve in the early portion of the experiment was a good indicator of how rapidly inversion occurred.
- the torque typically levelled off to form a plateau region. Higher levels of torque in the plateau region indicated a higher emulsion viscosity.
- Examples 4a-4c demonstrated that blends of anionic emulsion polymers comprising a 4-octyloxyphenol ethoxylate surfactant (with an appropriate moles of EO) provided improved performance over the blends of anionic emulsion polymers comprising an equivalent amount of linear alcohol ethoxylates (Activators 2 and 3) in both fresh water and high TDS water.
- the surfactants can be substituted for linear alcohol ethoxylates (Activators 2 and 3) that are currently used as activator for anionic emulsion polymer formulations.
- a standard 8:2 acrylamide/Acrylic acid emulsion co-polymer (emulsion polymer 7) without activating surfactant was used in this example.
- Anionic inverse emulsion polymers are used for friction reducing applications in oil and gas industries, more particularly during hydraulic fracturing to reduce pumping requirements. All evaluations with polymer 7 blends were done using torque method, and flow-loop experiments (described below) in high (12.3%) TDS brine. A series of three experiments was conducted.
- TDS Brine The 12.3% TDS brine used in this example was formed by blending the components of Table 18. Brine was filtered through a WHATMAN 1 filter by suction filtration to remove any particulate. Table 18. Ingredients of 12.3% TDS Brine Reagent Amount (g) NaCl 91.83 CaCl 2 2H 2 O 21.60 MgCl 2 6H 2 O 7.71 KCl 0.908 SrCl 2 6H 2 O 1.179 DI water 876.77
- Figure 26 depicts the inversion torque profile (0.5% invert in 12.3% TDS brine) for polymer 7 with approximately 2.5-4% activating surfactant.
- the rate of inversion for polymer 6 with 2.5% 4OP-8EO and 4% activator 3 were similar.
- the rate of inversion was faster for polymer 7 with all ethoxylated surfactants (4OP-nEO) than for polymer 7 with activator 3 at 2.5% (equivalent activator) concentrations.
- Emulsion polymer 7 was weighed into a 118.3 ml (4 oz.) bottle.
- Polymer 7 activator blends with indicated percent activator were made by blending activator into the emulsion while stirring. The resulting blends were stirred for one hour and allowed to stand for at least two hours before testing.
- Table 17 Polymer 7 blends with activating surfactants Activator Weight Emulsion 7 (g) Weight Activator (g) Wt.
- Figure 27 depicts an inversion torque profile (0.5% invert in 12.3% TDS brine) for polymer 7 with approximately 1.5-4% activators.
- the rate of inversion for polymer 7 with 2.0%, 2.5%, and 3.0% 4OP-8EO and 4% activator 3 were comparable.
- Figure 28 shows a comparison of the 2 minute percent inversion of polymer 7 with activating surfactants.
- the 2 minute percent inversion for polymer 7 with 4% activator 3 was greater than for the other polymers.
- Figure 29 shows a comparison of the 5 minute percent inversion of polymer 7 with activating surfactants.
- the 5 minute percent inversion for polymer 7 with 4OP-7.2EO was greater than for the other polymers.
- Figure 30 shows a comparison of the friction reduction properties of polymer 7 blends with 4% activator 3 and 1.5%, 2.0%, 2.5%, and 3.0% 4OP-8EO measured by flow loop tests in high TDS brine (13.4% TDS) at room temperature.
- Figure 31 shows a comparison of the friction reduction properties of polymer 7 blend with 4% activator 3 and 3.0% 4OP-8EO measured by flow loop tests in high TDS brine (13.4% TDS) at 40°F.
- polymer 7 blends with 4% Activator 3 and 3.0% 4OP-8EO showed similar friction reduction, i.e., about 70% friction reduction within one minute.
- polymer 7 blends with 3.0% 4OP-8EO showed better friction reduction (about 70% within two minutes) compared to 4% Activator 3 (about 60% within two minutes).
Description
- Surfactants capable of releasing and/or dissolving polymers to form water-soluble or water-dispersible polymer solutions are disclosed. In addition, polymer compositions containing a water-in-oil emulsion comprising the surfactant are provided and can be used, for example, in methods of dissolving a polymer. These surfactants and polymer compositions can be used in various industries including for water clarification, papermaking, sewage and industrial water treatment, drilling mud stabilizers, and enhanced oil recovery.
- Various synthetic and naturally-occurring water-soluble or water-dispersible polymers can be used in a variety of commercial applications. These polymers are commercially available as powders, finely-divided solids, or water-in-oil emulsion polymers that require the polymer to be dissolved in water. While the polymers are water-soluble or water-dispersible, it can be difficult to prepare solutions or homogeneous dispersions because of slow dissolution or slow dispersion into the water. Further, polymers can clump or remain as agglomerates on contact with water. Although these clumps eventually dissolve or disperse using agitation, it can be impractical to agitate the solution for a sufficiently long time to obtain complete dissolution of the polymer particles.
- Additionally, surfactants, and compositions thereof, can invert and/or activate water-in-oil emulsion polymers to aid the dissolution and dispersion of those polymers. Such inversion surfactants can be used to increase the dissolution of various emulsion polymers so the time for dissolution and degree of dissolution of the polymer is increased.
- To reduce the time needed for polymer solids or inverse emulsion polymers to dissolve or disperse in aqueous solution, an inversion surfactant can be used.
- Ethoxylated alkylphenols and alkylphenol-formaldehyde resins, particularly containing nonylphenol moiety as one of the building blocks have been used in the industry as one class of inversion surfactants.
GB2146260 - Because of the toxicity of nonylphenols and their ethoxylated derivatives, industrial use has largely shifted to linear/branched alcohol ethoxylates (LAEs). However, LAEs are generally not as effective as nonylphenol ethoxylates. Therefore, a need exists for novel inversion surfactants that are effective for dissolving or dispersing water-soluble or water-dispersible polymers in several industries.
- A polymer composition is provided that includes a water-in-oil emulsion containing an aqueous phase including water and a water-soluble or water-dispersible polymer, and an oil phase including an oil and an emulsifying agent; and an inversion surfactant having the structure of Formula 1:
- A polymer composition is also provided that includes a water-in-oil emulsion including an aqueous phase containing water and a water-soluble or water-dispersible polymer, an oil phase containing an oil and an emulsifying agent, and an inversion surfactant having the structure of Formula 1:
- A polymer composition is further provided that includes a water-in-oil emulsion containing an aqueous phase including water and a water-soluble or water-dispersible polymer, and an oil phase containing an oil and an emulsifying agent; and an aqueous solution containing an inversion surfactant having the structure of Formula 1:
- A polymer composition is also provided that comprises a water-soluble or water-dispersible polymer, an oil, a suspending agent, and a surfactant having the structure of Formula 1:
- Preferably, for the polymer composition described herein, in the inversion surfactant having the structure of
Formula 1, X is -O-. - Further, for the inversion surfactant having the structure of Formula 1, n can be an integer from 2 to 20. Preferably, n is an integer from 4 to 16. More preferably, n is an integer from 4 to 10.
- For the inversion surfactant having the structure of
Formula 1, R4 can be C4-C16 alkyl; R4 can also be C4-C12 alkyl; preferably, R4 is C8-C12 alkyl; and more preferably, R4 is octyl. - In the inversion surfactant having the structure of
Formula 1, R3, R5, R9, and R10 can independently be hydrogen or methyl, and preferably, R3, R5, R9, and R10 are hydrogen. - Additionally, R6 can be hydrogen, methyl, butyl, or benzyl, or a combination thereof. For example, R6 can be methyl, hydrogen, or a combination thereof. Preferably, R6 can be hydrogen.
- For the structure of Formula 1, R11 can be hydrogen or alkyl; preferably, hydrogen or methyl; most preferably, hydrogen.
- In the described polymer composition, the inversion surfactant having the structure of Formula 1 can have a concentration of from about 0.1 wt.% to about 10 wt.% based on the total weight of the polymer composition. Preferably, the inversion surfactant having the structure of Formula 1 has a concentration of from about 0.5 wt.% to about 5 wt.% based on the total weight of the polymer composition.
- The polymer composition can comprise from about 5 wt.% to about 70 wt.%, of the water-soluble or water-dispersible polymer. Preferably, the polymer composition comprises from about 18 wt.% to about 65 wt.% of the water-soluble or water-dispersible polymer.
- A method of dissolving the water-soluble or water-dispersible polymer of the polymer composition is also provided, the method comprising contacting the water-in-oil emulsion with the inversion surfactant having the structure of
Formula 1. - A further method of dissolving the water-soluble or water-dispersible polymer of the polymer composition is also provided, the method comprising contacting the water-in-oil emulsion further comprising the inversion surfactant having the structure of
Formula 1 with an aqueous solution. - Another method of dissolving the water-soluble or water-dispersible polymer of the polymer composition is provided, the method comprising contacting the water-in-oil emulsion with an aqueous solution comprising the inversion surfactant having the structure of
Formula 1. - The polymer composition or methods described herein can have the polymer composition further comprise an ethoxylated C10-C16 alcohol; a C12-C13 primary alcohol of linear and mono-methyl branched alcohol having on average 9 moles ethylene oxide; an ethoxylate of a saturated C12-15 alcohol; an ethoxylated C12-14 alcohol; an ethoxylated primary branched saturated C13 alcohol; an ethoxylated C10 Guerbet alcohol; an ethoxylated saturated iso-C13 alcohol; a saturated, predominantly unbranched C13-15 oxo alcohol having 11 ethylene oxide groups; a secondary alcohol ethoxylate; a nonionic, alkoxylated alcohol; a polyoxyethylene (9) synthetic primary C13/C15 alcohol; an isotridecyl alcohol ethoxylated with an average of 9 moles ethylene oxide; an ethoxylated linear primary C12-14 alcohol; an ethoxylated nonylphenol; tert-octylphenoxypoly(ethoxyethanol); a tridecyl ether phosphate; a polyoxyethylene (5) soyaallylamine; a polyethylene glycol (PEG) 400 monooleate; a
PEG 600 monooleate; aPEG-25 castor oil; a PEG-30 castor oil; a PEG-40 castor oil; an aliphatic phosphate ester with 10 moles EO; an aliphatic phosphate ester with 6 moles EO; an oleic acid monoethanol amide with 14 moles ethylene oxide; a soyamine ethoxylate; or a combination thereof. - The methods described herein can have the inversion surfactant be activated by contacting the inversion surfactant with an inversion aid.
- For the methods described herein, the inversion aid can comprise glycol, , a polypropylene glycol, polyglycerol, urea, sorbitol, sucrose, glycerol, a polyglycerol, a phosphate, choline chlorine, guanidine, dioctyl-sulfosuccinate, malic acid, lactic acid, N-(phosphonomethyl)glycine, 2-phosphonopropanoic acid, 3-phosphonopropanoic acid, 4-phosphonobutanoic acid, a phosphinosuccinic oligomer, or a combination thereof.
- The inversion surfactant can be activated by contacting the inversion surfactant with an aqueous solution. Further, the aqueous solution can contain a salt.
- The inversion surfactant can be activated by increasing the temperature of the aqueous solution, and preferably, the temperature of the aqueous solution is increased from about 10°C to about 65°C.
- A compound is also provided that has the structure of Formula 2:
- Preferably, the compound having the structure of
formula 2 has R3, R5, R9, and R10 are hydrogen; R4 is C8-C16 branched alkyl; R6 and R11 are hydrogen; X is -O-; and n is an integer from 1 to 20. - Other objects and features will be in part apparent and in part pointed out hereinafter.
-
-
Figure 1 is a graph of the torque versus time and shows the inversion torque profile (0.5% invert) forpolymer 1 with approximately 1% activating surfactant. -
Figure 2 is a graph of the torque versus time and shows the inversion torque profile (0.5% invert) forpolymer 1 with approximately 1.2% activating surfactant. -
Figure 3 is a graph of the torque versus time and shows the inversion torque profile (0.5% invert) forpolymer 1 with approximately 1.4% activating surfactant. -
Figure 4 is a graph of the percent inversion versus the percent activating surfactant and shows a comparison of the 2 minute percent inversion ofpolymer 1 with the activating surfactants. -
Figure 5 is a graph of the percent inversion versus the percent activating surfactant and shows a comparison of the 5 minute percent inversion ofpolymer 1 with the activating surfactants. -
Figure 6 is a graph of the torque versus time and shows the inversion torque profile (2% invert in DI water) forpolymer 2 with approximately 2% activating surfactant. -
Figure 7 is a graph of the torque versus time and shows the inversion torque profile (2% invert in DI water) forpolymer 2 with approximately 2.5% activating surfactant. -
Figure 8 is a graph of the torque versus time and shows the inversion torque profile (2% invert in DI water) forpolymer 2 with approximately 3% activating surfactant. -
Figure 9 is a graph of the percent inversion versus the percent activating surfactant and shows a comparison of the 2 minute percent inversion ofpolymer 2 with activating surfactants. -
Figure 10 is a graph of the percent inversion versus the percent activating surfactant and shows a comparison of the 5 minute percent inversion ofpolymer 2 with activating surfactants. -
Figure 11 is a graph of the percent inversion versus the percent activating surfactant and the inversion torque profile (2% invert) forpolymer 3 with approximately 1.5% activating surfactant. -
Figure 12 is a graph of the percent inversion versus the percent activating surfactant and shows the inversion torque profile (2% invert) forpolymer 3 with approximately 1.8% activating surfactant. -
Figure 13 is a graph of the percent inversion versus the percent activating surfactant and shows the inversion torque profile (2% invert) forpolymer 3 with approximately 2.1% activating surfactant. -
Figure 14 is a graph of the percent inversion versus the percent activating surfactant and the inversion torque profile (2% invert) forpolymer 3 with approximately 2.4% activating surfactant. -
Figure 15 is a graph of the percent inversion versus the percent activating surfactant and shows a comparison of the 2 minute percent inversion ofpolymer 3 with activating surfactants. -
Figure 16 is a graph of the percent inversion versus the percent activating surfactant and shows a comparison of the 5 minute percent inversion ofpolymer 3 with activating surfactants. -
Figure 17 is a graph of the torque versus time and shows the inversion torque profile (0.5% invert in tap water) forpolymer 4 with approximately 1.35% activating surfactant. -
Figure 18 shows a comparison of the 2 minute percent inversion ofpolymer 4 with activating surfactants. -
Figure 19 shows a comparison of the 5 minute percent inversion ofpolymer 4 with activating surfactants. -
Figure 20 is a graph of the torque versus time and shows the inversion torque profile (1% invert in SSW) forpolymer 4 with approximately 2.5% activating surfactant. -
Figure 21 shows a comparison of the 2 minute percent inversion of polymer 5 with activating surfactants. -
Figure 22 shows a comparison of the 5 minute percent inversion of polymer 5 with activating surfactants. -
Figure 23 is a graph of the torque versus time and shows the inversion torque profile (1% invert in SSW) forpolymer 6 with approximately 2.0% activating surfactant. -
Figure 24 shows a comparison of the 2 minute percent inversion ofpolymer 6 with activating surfactants. -
Figure 25 shows a comparison of the 5 minute percent inversion ofpolymer 6 with activating surfactants. -
Figure 26 is a graph of the torque versus time and shows the inversion torque profile (0.5% invert in 12.3% TDS brine) forpolymer 7 with approximately 2.5-4% activating surfactant. -
Figure 27 is a graph of the torque versus time and shows an inversion torque profile (0.5% invert in 12.3% TDS brine) forpolymer 7 with approximately 1.5-4% activators. -
Figure 28 shows a comparison of the 2 minute percent inversion ofpolymer 7 with activating surfactants. -
Figure 29 shows a comparison of the 5 minute percent inversion ofpolymer 7 with activating surfactants. -
Figure 30 is a graph of the percent friction reduction versus time and shows a comparison of the friction reduction properties ofpolymer 7 blends with 4% activator 3 and 1.5%, 2.0%, 2.5%, and 3.0% 4OP-8EO measured by flow loop tests in high TDS brine (13.4% TDS) at room temperature. -
Figure 31 is a graph of the percent friction reduction versus time and shows a comparison of the friction reduction properties ofpolymer 7 blend with 4% activator 3 and 3.0% 4OP-8EO measured by flow loop tests in high TDS brine (13.4% TDS) at 40°F. - Corresponding reference characters indicate corresponding parts throughout the drawings.
- Inversion surfactants are provided that can dissolve water-soluble or water-dispersible polymers rapidly and completely in aqueous solution. The polymer compositions containing the surfactants described herein can be used in various industries including for water clarification, papermaking, sewage and industrial water treatment, drilling mud stabilizers, and enhanced oil recovery.
- Polymer compositions including water-in-oil emulsions and inversion surfactants are provided. Also, methods of dissolving a water-soluble or water-dispersible polymer are disclosed.
- Therefore, polymer compositions and methods using the polymer compositions are described herein. The polymer composition comprises a water-in-oil emulsion comprising an aqueous phase comprising water and a water-soluble or water-dispersible polymer, and an oil phase comprising an oil and an emulsifying agent; and an inversion surfactant having the structure of Formula 1:
- A polymer composition is further provided that includes a water-in-oil emulsion containing an aqueous phase comprising water and a water-soluble or water-dispersible polymer, and an oil phase comprising an oil and an emulsifying agent; and an aqueous solution containing an inversion surfactant having the structure of Formula 1:
- A polymer composition is also provided that comprises a water-soluble or water-dispersible polymer, an oil, a suspending agent, and a surfactant having the structure of Formula 1:
- A compound is also provided that has the structure of Formula 2:
- Preferably, the compound having the structure of
formula 2 has R3, R5, R9, and R10 are hydrogen; R4 is C8-C16 branched alkyl; R6 and R11 are hydrogen; X is -O-; and n is an integer from 1 to 20. - Preferably, in the inversion surfactant of
Formula - Further, in the inversion surfactant of
Formula - For the inversion surfactant of
Formula 1, R4 can be C4-C16 alkyl; R4 can also be C4-C12 alkyl; preferably, R4 is C8-C12 alkyl; and more preferably, R4 is octyl. - In the inversion surfactant of
Formula - Additionally, for the inversion surfactant of
Formula - For the inversion surfactant of
Formula - The polymer composition can comprise from about 5 wt.% to about 70 wt.%, from about 10 wt.% to about 70 wt.%, from about 20 wt.% to about 70 wt.%, from about 30 wt.% to about 70 wt.%, from about 40 wt.% to about 70 wt.%, from about 50 wt.% to about 70 wt.%, from about 60 wt.% to about 70 wt.%, from about 10 wt.% to about 60 wt.%, from about 10 wt.% to about 50 wt.%, from about 15 wt.% to about 70 wt.%, from about 15 wt.% to about 65 wt.%, from about 18 wt.% to about 65 wt.%, from about 20 wt.% to about 60 wt.%, from about 20 wt.% to about 50 wt.%, from about 25 wt.% to about 70 wt.%, from about 25 wt.% to about 60 wt.%, from about 25 wt.% to about 50 wt.%, of the water-soluble or water-dispersible polymer. Preferably, the polymer composition comprises from about 18 wt.% to about 65 wt.% of the water-soluble or water-dispersible polymer.
- The polymer composition can be a slurry comprising a water-soluble polymer suspended in an oil-based vehicle with a suspension agent and a surfactant of
Formula - Specifically, the oil-based vehicle can be petroleum distillate. Petroleum distillates are products distilled from petroleum crude oil and use different CAS # identifiers depending upon the molecular weight distribution and processing technology used. A petroleum distillate suitable for the present composition can be, for example, CAS #64742-47-8.
- The suspension aid can be a variation of diblock copolymers based on styrene and ethylene/propylene. The composition can also contain a dispersant such as organophilic clay or a synthetic alternative as the suspension agent.
- The inversion surfactant having the structure of
Formula Trade Name Chemistry Alfonic 1412-7 Ethoxylated C10-C16 alcohols Novel 23E9 C12-C13 primary alcohol of linear and mono-methyl branched alcohols having on average 9 moles EO Synperonic A11 Ethoxylate of a saturated C12-15 alcohol Surfonic 1412-12 Ethoxylated C12-14 alcohol Synperonic 13/7 Ethoxylated primary branched saturated C13 alcohol Lutensol TO10 Ethoxylated C10 Guerbet alcohol Lutensol TO12 Ethoxylated saturated iso-C13 alcohol Lutensol AO11 Saturated, predominantly unbranched C13-15 oxo alcohols having 11 EO groups Tergitol 15-S-9 Secondary Alcohol Ethoxylate Tergitol 15-S-12 Secondary Alcohol Ethoxylate Plurafac RA 20 Nonionic, alkoxylated alcohol Plurafac RA 30 Nonionic, alkoxylated alcohol Synperonic A9 Polyoxyethylene (9) synthetic primary C13/C15 alcohol Alfonic TDA9 Isotridecyl alcohol ethoxylated with an average of 9 moles EO Novel 1412-11 Ethoxylated linear primary C12-14 alcohol Tergitol NP-9.5 Ethoxylated nonylphenol Tergitol NP-10.5 Ethoxylated nonylphenol Triton X-114 tert-octylphenoxypoly(ethoxyethanol) Rhodafac RS-410 Tridecyl ether phosphate Ethomeen S/15 Polyoxyethylene (5) soyaallylamines Ethox MO-9 PEG 400 monooleate Ethox MO-14 PEG 600 monooleate Ethox CO-25 PEG-25 Castor oil Alkamul EL-620 PEG-30 Castor oil Ethox CO-40 PEG-40 Castor oil Rhodafac RS-710 Aliphatic phosphate ester, 10 moles EO Rhodafac RS-610 Aliphatic phosphate ester, 6 moles EO Serdox NXC-14 Oleic acid monoethanol amide + 14 EO Ethomeen S/25 Soyamine ethoxylate - The inversion surfactant having the structure of
Formula PEG 600 monooleate; aPEG-25 castor oil; a PEG-30 castor oil; a PEG-40 castor oil; an aliphatic phosphate ester with 10 moles EO; an aliphatic phosphate ester with 6 moles EO; an oleic acid monoethanol amide with 14 moles ethylene oxide; a soyamine ethoxylate; or a combination thereof. - The methods described herein, wherein the inversion surfactant is activated by contacting the inversion surfactant with an inversion aid.
- The methods described herein, wherein the inversion aid comprises glycol, a polyethylene glycol, a polypropylene glycol, polyglycerol, urea, sorbitol, sucrose, glycerol, a phosphate, choline chlorine, guanidine, dioctyl-sulfosuccinate, malic acid, lactic acid, N-(phosphonomethyl)glycine, 2-phosphonopropanoic acid, 3-phosphonopropanoic acid, 4-phosphonobutanoic acid, a phosphinosuccinic oligomer or a combination thereof.
-
- In the described polymer composition, the inversion surfactant having the structure of
Formula 1 can have a concentration of from about 0.1 wt.% to about 10 wt.% based on the total weight of the polymer composition. Preferably, the inversion surfactant having the structure ofFormula 1 has a concentration of from about 0.5 wt.% to about 5 wt.% based on the total weight of the polymer composition. - The water-in-oil polymer emulsion can further comprise an emulsifying agent. The surfactant or blend of surfactants can have a low hydrophile-lipophile balance (HLB) to aid preparation of an oil-continuous emulsion. Appropriate surfactants for water-in-oil emulsion polymerizations which are commercially available are compiled in the North American Edition of McCutcheon's Emulsifiers & Detergents. For example, the emulsifying agent can comprise nonionic ethoxylated fatty acid esters, ethoxylated sorbitan fatty acid esters, sorbitan esters of fatty acids such as sorbitan monolaurate, sorbitan monostearate, and sorbitan monooleate, block copolymers of ethylene oxide and hydroxyacids having a C10-C30 linear or branched hydrocarbon chain, linear or branched alcohol alkoxylates, or a combination thereof.
- The emulsifying agent can be a single nonionic surfactant or blend thereof having a combined HLB value of about 2 to 10, for example about 3 to 10, or about 4 to 10, or about 5 to 10, or about 6 to 10, or about 7 to 10, or about 8 to 10, or about 2 to 9, or about 2 to 8, or about 2 to 7, or about 2 to 6, or about 2 to 5, or about 3 to 9, or about 4 to 8.
- The water-in-oil emulsion can also comprise an alcohol alkoxylate. The alcohol alkoxylate can comprise a linear or branched alcohol ethoxylate, or a combination thereof.
- The surfactant compositions, as described above, are useful as inverters (activators) of water-in-oil (inverse) emulsion polymers in various industries including for water clarification, papermaking, sewage and industrial water treatment, drilling mud stabilizers, and enhanced oil recovery.
- The water-soluble or water-dispersible polymers useful in the polymer compositions include various polymers and their mixtures, or derivatives. The water-soluble or water-dispersible polymers used can be an anionic, a cationic, a nonionic, a zwitterionic, or an amphoteric polymer.
- For example, the water-soluble or water-dispersible polymers contained in the polymer compositions can comprise polyacrylamides, polyacrylates, copolymers thereof, and hydrophobically modified derivatives of these polymers.
- Further, the water-soluble or water-dispersible polymers used in the polymer compositions described herein can include the water-soluble or water-dispersible polymers described in
U.S. Patent Nos. 3,624,019 and3,734,873 ; the water-soluble or water-dispersible polymers can have various architectures as disclosed inEP 202780 EP 374458 U.S. Patent Nos. 5,945,494 and5,961,840 (branched) . Additionally, the water-soluble or water-dispersible polymers can contain hydrophobic monomers as disclosed inU.S. Patent No. 4,918,123 . - The polymers usefully incorporated in the polymer compositions typically have a weight average molecular weight (Mw) of about 500,000 Daltons to about 100,000,000 Daltons, or about 1,000,000 Daltons to about 50,000,000 Daltons, or about 5,000,000 Daltons to about 30,000,000 Daltons.
- The water-soluble or water-dispersible polymer can comprise about 1 mol% to about 100 mol% acrylamide monomers, or about 1 mol % to about 90 mol %, or about 1 mol % to about 80 mol %, or about 1 mol % to about 70 mol %, or about 1 mol % to about 60 mol %, or about 1 mol % to about 50 mol %, or about 1 mol % to about 40 mol %, or about 1 mol % to about 30 mol %, or about 1 mol % to about 20 mol %, or about 1 mol % to about 10 mol %, or about 10 mol % to about 100 mol %, or about 20 mol % to about 100 mol %, or about 30 mol % to about 100 mol %, or about 40 mol % to about 100 mol %, or about 50 mol % to about 100 mol %, or about 60 mol % to about 100 mol %, or about 70 mol % to about 100 mol %, or about 80 mol % to about 100 mol %, or about 90 mol % to about 100 mol %, or about 20 mol % to about 80 mol, or about 30 mol % to about 70 mol %, or about 40 mol % to about 60 mol %, or about 60 mol % to about 80 mol % acrylamide monomers.
- The water-soluble polymer or water-dispersible polymer can be present within the water-in-oil emulsion at about 15 wt % to 70 wt%, or about 17 wt % to 70 wt %, or about 19 wt % to 70 wt%, or about 21 wt% to 70 wt%, or about 23 wt % to 70 wt %, or about 25 wt % to 70 wt %, or about 15 wt % to 68 wt%, or about 15 wt% to 66 wt%, or about 15 wt % to 64 wt%, or about 15 wt% to 62 wt%, or about 15 wt % to 60 wt%, or about 15 wt% to 58 wt%, or about 15 wt % to 56 wt%, or about 25 wt% to 65 wt%, or about 30 wt % to 60 wt %, or about 30 wt % to 60 wt % based on the total weight of the emulsion.
- Inverse emulsion polymers are prepared by dissolving the required monomers in the water phase, dissolving the emulsifying agent in the oil phase, emulsifying the water phase in the oil phase to prepare a water-in-oil emulsion, homogenizing the water-in-oil emulsion and polymerizing the monomers to obtain the polymer. A self-inverting surfactant may be added to the water-soluble polymer dispersed within the hydrocarbon matrix to obtain a self-inverting water-in-oil emulsion. Alternatively, a polymer solution can be made-up by inverting the polymer dispersed in oil in to water containing the surfactant.
- Also present in the water-in-oil emulsion is an amount of water sufficient to form an aqueous (i.e. water) phase within the emulsion. Water is present in the water-in-oil emulsion at about 3 wt % to 50 wt %, or about 5 wt% to 50 wt%, or about 10 wt% to 50 wt%, or about 15 wt% to 50 wt%, or about 20 wt % to 50 wt %, or about 25 wt % to 50 wt %, or about 3 wt % to 35 wt %, or about 3 wt % to 30 wt %, or about 3 wt % to 25 wt %, or about 5 wt % to 45 wt %, or about 5 wt % to 40 wt %, or about 5 wt % to 35 wt %, based on the total weight of the water-in-oil emulsion.
- The water-in-oil emulsion also contains an amount of oil sufficient to form an oil phase within the water-in-oil emulsion.
- The oil in the oil phase can be a mixture of compounds, wherein the mixture is less than 0.1 wt % soluble in water at 25° C and is a liquid over the range of 20° C to 90° C.
- The oil in the oil phase can comprise a linear, branched, or cyclic hydrocarbon moieties, aryl or alkaryl moieties, or combinations thereof.
- The oil in the oil phase can have a density of about 0.8 g/L to 1.0 g/L, for example about 0.8 g/L to 0.9 g/L.
- Examples of suitable oils for the oil phase can include a petroleum distillate, decane, dodecane, isotridecane, cyclohexane, toluene, xylene, and mixed paraffin solvents such as those sold under the trade name ISOPAR® by ExxonMobil Corp. of Irving, Texas.
- The oil phase is present in the water-in-oil emulsion at about 10 wt% to 40 wt %, or about 15 wt % to 40 wt %, or about 20 wt % to 40 wt %, or about 22 wt % to 40 wt %, or about 24 wt % to 40 wt %, or about 26 wt % to 40 wt %, or about 28 wt % to 40 wt %, or about 30 wt % to 40 wt %, or about 10 wt % to 38 wt %, or about 10 wt% to 36 wt%, or about 10 wt% to 34 wt%, or about 10 wt% to 32 wt%, or about 10 wt% to 30 wt%, or about 10 wt% to 25 wt%, or about 10 wt% to 20 wt%, or about 15 wt % to 35 wt %, or about 20 wt % to 30 wt % based on the total weight of the water-in-oil emulsion.
- The inversion surfactant of Formula I aids the inversion of the water-in-oil emulsion compared to a water-in-oil emulsion comprising no inversion surfactant or compared to a water-in-oil emulsion comprising a comparator inversion surfactant. The inversion surfactant of Formula I, of the present disclosure increase the speed and/or percent completion of the inversion process compared to a water-in-oil emulsion comprising no inversion surfactant or compared to a water-in-oil emulsion comprising a comparator inversion surfactant.
- To aid inversion of a water-in-oil emulsion, the inversion surfactant is added to the emulsion at about 0.1 wt% to 20.0 wt% based on the total weight of the emulsion, or about 0.1 wt% to 15.0 wt%, or about 0.1 wt% to 10.0 wt%, or about 0.1 wt% to 7.5 wt%, or about 0.1 wt % to 5.0 wt%, or about 0.5 wt% to 4.5 wt%, or about 1.0 wt% to 4.0 wt%, or about 1.5 wt% to 3.5 wt%, or about 2.0 wt% to 3.0 wt%, or about 0.1 wt% to 4.5 wt%, or about 0.1 wt% to 4.0 wt%, or about 0.1 wt% to 3.5 wt%, or about 0.1 wt% to 3.0 wt%, or about 0.5 wt% to 5.0 wt%, or about 1.0 wt% to 5.0 wt%, or about 1.5 wt% to 5.0 wt%, or about 2.0 wt% to 5.0 wt%, based on the total weight of the emulsion.
- The inversion surfactant can be added to the aqueous solution contacted with the emulsion to activate the polymer in a concentration of about 0.1 wt% to 20.0 wt% based on the total weight of the aqueous solution, or about 0.1 wt% to 15.0 wt%, or about 0.1 wt% to 10.0 wt%, or about 0.1 wt% to 7.5 wt%, or about 0.1 wt % to 5.0 wt%, or about 0.5 wt% to 4.5 wt%, or about 1.0 wt% to 4.0 wt%, or about 1.5 wt% to 3.5 wt%, or about 2.0 wt% to 3.0 wt%, or about 0.1 wt% to 4.5 wt%, or about 0.1 wt% to 4.0 wt%, or about 0.1 wt% to 3.5 wt%, or about 0.1 wt% to 3.0 wt%, or about 0.5 wt% to 5.0 wt%, or about 1.0 wt% to 5.0 wt%, or about 1.5 wt% to 5.0 wt%, or about 2.0 wt% to 5.0 wt%, based on the total weight of the aqueous solution.
- The effective amount of the polymer composition can be from about 1 ppm to about 10000 ppm, from about 1 ppm to about 9000 ppm, from about 1 ppm to about 8000 ppm, from about 1 ppm to about 7000 ppm, from about 1 ppm to about 6000 ppm, from about 1 ppm to about 5000 ppm, from about 1 ppm to about 4000 ppm, from about 1 ppm to about 3000 ppm, from about 1 ppm to about 2000 ppm, from about 1 ppm to about 1000 ppm, based on the total weight of the process fluid. Preferably, the effective amount of the polymer composition is from about 1 ppm to about 900 ppm, from about 1 ppm, to about 800 ppm, from about 1 ppm to about 700 ppm, from about 1 ppm to about 600 ppm, or from about 1 ppm to about 500 ppm. Further, the effective amount of the polymer composition can be from about 1 ppm to about 250 ppm, from about 1 ppm to about 200 ppm, from about 1 ppm to about 100 ppm, from about 1 ppm to about 75 ppm, from about 1 ppm to about 50 ppm, from about 1 ppm to about 25 ppm, from about 1 ppm to about 15 ppm, or from about 1 ppm to about 10 ppm, based on the total weight of the process fluid.
- The inversion and dilution to a target concentration of less than 1 wt % can be accomplished in about 1 to 15 minutes, for example about 1 to 14, 1 to 13, 1 to 12, 1 to 11, 1 to 10, 1 to 9, 1 to 8, 1 to 7, 1 to 6, 1 to 5, 2 to 15, 3 to 15, 4 to 15, 5 to 15, 6 to 15, 7 to 15, 8 to 15, 9 to 15, 10 to 15, 2 to 10, 2 to 9, 2 to 8, 2 to 7, 2 to 6, or 2 to 5 minutes.
- After inversion, the aqueous solutions can comprise about 100 ppm to 10,000 ppm (0.01 wt% to 1.00 wt%) water-soluble or water-dispersible polymer, or about 200 ppm to 5000 ppm, or about 200 ppm to 4000 ppm, or about 200 ppm to 3000 ppm, or about 200 ppm to 2500 ppm water-soluble or water-dispersible polymer, based on the total weight of the aqueous solution.
- As used herein, the term "polymer" means a water-soluble or water-dispersible polymer. The term "polymer" encompasses and includes homopolymers, copolymers, terpolymers and polymers with more than three monomers, crosslinked or partially crosslinked polymers, and combinations or blends of these.
- As used herein, the term "polymer solution" or "polymer dispersion" means a polymer composition substantially dispersed or dissolved in water, a water source, or a water-based solution. Water-based solutions include one or more dissolved salts, buffers, acids, bases, surfactants, or other dissolved, dispersed, or emulsified compounds, materials, components, or combinations thereof.
- As used herein, "inverse emulsion polymer" and "inverse latex polymer" mean a water-in-oil polymer emulsion comprising a water-soluble polymer (which could be cationic, anionic, nonionic, amphoteric polymer, or zwitterionic) according to this invention in the aqueous phase, a hydrocarbon oil for the oil phase and a water-in-oil emulsifying agent. Inverse emulsion polymers are hydrocarbon continuous with the water-soluble polymers dispersed within the hydrocarbon matrix. The inverse emulsion polymers are then "inverted" or activated for use by releasing the polymer from the particles using shear, dilution, and generally another surfactant. See
U.S. Pat. No. 3,734,873 . - As used herein, the term "water source" means a source of water comprising, consisting essentially of, or consisting of fresh water, deionized water, distilled water, produced water, municipal water, waste water such as runoff water or municipal waste water, treated or partially treated waste water, well water, brackish water, "gray water", sea water, or a combination of two or more such water sources as determined by context. A water source can include one or more salts, ions, buffers, acids, bases, surfactants, or other dissolved, dispersed, or emulsified compounds, materials, components, or combinations thereof.
- As used herein, the terms "water-in-oil emulsion" mean a discontinuous internal water phase within a continuous oil phase, wherein the water phase includes at least one monomer or polymer. In general and as determined by context, these terms denote an emulsion prior to addition of inversion surfactants.
- As used herein, the term "oil" or "hydrocarbon solvent" as applied to an oil phase of a water-in-oil emulsion, means any compound or blend thereof that is less than 0.1 wt % soluble in water at 25° C., is substantially chemically inert within a water-in-oil emulsion as described herein, and is a liquid over at least the range of 20° C. to 100° C.
- As used herein, the term "water phase" means a water source having at least a monomer or polymer dispersed or dissolved therein, further wherein the dispersion or solution is a discontinuous phase within a water-in-oil emulsion.
- Unless otherwise indicated, an alkyl group as described herein alone or as part of another group is an optionally substituted linear saturated monovalent hydrocarbon substituent containing from one to sixty carbon atoms and preferably one to thirty carbon atoms in the main chain or eight to thirty carbon atoms in the main chain, or an optionally substituted branched saturated monovalent hydrocarbon substituent containing three to sixty carbon atoms, and preferably eight to thirty carbon atoms in the main chain. Examples of unsubstituted alkyl groups include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, i-pentyl, s-pentyl, t-pentyl, and the like.
- The terms "aryl" or "ar" as used herein alone or as part of another group (e.g., arylalkyl) denote optionally substituted homocyclic aromatic groups, preferably monocyclic or bicyclic
groups containing form 6 to 12 carbon atoms in the ring portion, such as phenyl, biphenyl, naphthyl, substituted phenyl, substituted biphenyl, or substituted naphthyl. Phenyl and substituted phenyl are the more preferred aryl groups. The term "aryl" also includes heteroaryl functional groups. - "Arylalkyl" means an aryl group attached to the parent molecule through an alkylene group. The number of carbon atoms in the aryl group and the alkylene group is selected such that there is a total of about 6 to about 18 carbon atoms in the arylalkyl group. A preferred arylalkyl group is benzyl.
- The term "substituted," as in "substituted aryl," "substituted alkyl," and the like, means that in the group in question (i.e., the alkyl, aryl, or other group that follows the term), at least one hydrogen atom bound to a carbon atom is replaced with one or more substituent groups such as hydroxy (-OH), alkylthio, amido (-CON(RA)(RB), wherein RA and RB are wherein RA and RB are independently hydrogen, alkyl, or aryl), amino (-N(RA)(RB), wherein RA and RB are independently hydrogen, alkyl, or aryl), halo (fluoro, chloro, bromo, or iodo), silyl, nitro (-NO2), an ether (-ORA wherein RA is alkyl or aryl), an ester (-OC(O)RA wherein RA is alkyl or aryl), keto (-C(O)RA wherein RA is alkyl or aryl), heterocyclo, and the like. When the term "substituted" introduces a list of possible substituted groups, it is intended that the term apply to every member of that group. That is, the phrase "optionally substituted alkyl or aryl" is to be interpreted as "optionally substituted alkyl or optionally substituted aryl."
- The term "heterocyclo," "heterocycle," or "heterocyclyl," as used herein, refers to a monocyclic, bicyclic, or tricyclic group containing 1 to 4 heteroatoms selected from N, O, S(O)n, P(O)n, PRz, NH or NRz, wherein Rz is a suitable substituent. Heterocyclic groups optionally contain one or two double bonds. Heterocyclic groups include, but are not limited to, azetidinyl, tetrahydrofuranyl, imidazolidinyl, pyrrolidinyl, piperidinyl, piperazinyl, oxazolidinyl, thiazolidinyl, pyrazolidinyl, thiomorpholinyl, tetrahydrothiazinyl, tetrahydro-thiadiazinyl, morpholinyl, oxetanyl, tetrahydrodiazinyl, oxazinyl, oxathiazinyl, indolinyl, isoindolinyl, quinuclidinyl, chromanyl, isochromanyl, and benzoxazinyl. Examples of monocyclic saturated or partially saturated ring systems are tetrahydrofuran-2 yl, tetrahydrofuran-3-yl, imidazolidin-1-yl, imidazolidin-2 yl, imidazolidin-4-yl, pyrrolidin-1-yl, pyrrolidin-2 yl, pyrrolidin-3-yl, piperidin-1-yl, piperidin-2 yl, piperidin-3-yl, piperazin-1-yl, piperazin-2 yl, piperazin-3-yl, 1,3-oxazolidin-3-yl, isothiazolidine, 1,3-thiazolidin-3-yl, 1,2 pyrazolidin-2 yl, 1,3-pyrazolidin-1-yl, thiomorpholin-yl, 1,2 tetrahydrothiazin-2 yl, 1,3-tetrahydrothiazin-3-yl, tetrahydrothiadiazin-yl, morpholin-yl, 1,2 tetrahydrodiazin-2 yl, 1,3-tetrahydrodiazin-1-yl, 1,4-oxazin-2 yl, and 1,2,5 oxathiazin-4-yl. Heterocyclic groups can be unsubstituted or substituted by one or more suitable substituents, preferably 1 to 3 suitable substituents, as defined above.
- The following non-limiting examples are provided to further illustrate the present invention.
- The synthesis of 4-(octyloxy)phenol was completed using the reagents specified in Table 1 and according to the reaction depicted in
Scheme 1, wherein R is octyl and X is bromo.Table 1. Reagents for synthesis of 4-(octyloxyphenol) Reagent Molecular Weight (g/mol) Weight (g) Weight (mol) Mol reagent / mol hydroquinone Hydroquinone 110.11 200 1.82 1.00 1-bromooctane 193.12 293 1.52 0.84 Potassium hydroxide 56.10 100 2.00 0.98 Potassium iodide 166.02 0.2 0.001 Ethanol (reagent grade) 1200 -
- Dichloromethane, hexanes, distilled water, and concentrated hydrochloric acid were also used. Ethanol was charged to a 3-L four-necked reactor equipped with an overhead stirrer, nitrogen purge, temperature probe, a dropping funnel, and a condenser. The overhead stirrer was adjusted to a speed of approximately 500 rpm. A very slow nitrogen purge was started. Potassium hydroxide pellets were charged to the reactor. The reactor was heated to 40 °C and held for 30 minutes. Hydroquinone and potassium iodide were charged to the reactor and the reaction temperature was increased to 65°C.
- Into a dropping funnel was charged 1-bromooctane, which was added into the reactor over a period of three hours, while maintaining stirring and temperature of 65 °C. Stirring was continued at 65 °C until no 1-bromooctane was left in the solution as monitored by GC-MS. This process typically requires 8-10 hours.
- The reaction was subsequently cooled to room temperature and acidified to a pH of 2.0 with concentrated hydrochloric acid. Approximately 300 mL deionized (DI) water was added and the reaction mixture was stirred for 15 minutes. The reaction mixture was extracted twice with 20 mL dichloromethane. The combined organic phase was then washed three times with 200 mL DI water, dried over Na2SO4, and concentrated in vacuo to provide off-white solids. The crude solids were washed with minimum amounts of cold hexanes to provide pure 4-(octyloxy)phenol. The sample was dried in a 40°C oven.
- The following reagents and amounts thereof were used in the reaction: 570.00 g 4-(octyloxy)phenol of known concentration; 3.00 g potassium hydroxide (45% in water); about 30-35 mL heavy aromatic naphtha; ethylene oxide. The reaction proceeded according to
Scheme 3, wherein R represents octyl, m represents an integer from 4 to 75, and n represents an integer from 0 to 20. - To a 1 L four-necked round bottom flask was added 4-(octyloxy)phenol and potassium hydroxide; the flask was equipped with an overhead stirrer, an nitrogen purge, a Dean-Stark trap with condenser, and a temperature probe. The stirrer was started at moderate speed, as the nitrogen purge was started at a rate of one bubble per second. The water flow was turned on to the condenser and the Dean-Stark trap was filled to the neck with heavy aromatic naphtha. The temperature was set to 150 °C and heating was started.
- Water was distilled from the base catalyst. A 5 mL sample was collected for Karl-Fischer water analysis. If the sample contained more than 0.1% water, distillation was continued for 30 minutes and analysis was repeated.
- When the sample contained less than 0.1% water, the flask was cooled to 60°C. Once the reaction mixture reached 60°C, the N2 purge was increased. Under N2 purge, the contents of the flask were poured into a tared nitrogen-filled one quart bottle. The contents of the bottle were then transferred to the Lab Oxyalkylation Unit Paar Reactor. The Paar Reactor was buttoned up and purged with nitrogen from three to four times. The pressure was set to 0.34 bar (5 psi) with nitrogen.
- The reactor was heated to 150 °C. Once stabilized, ethylene oxide was added until the pressure reached 4.13 bar (60 psi). The weight of the ethylene oxide added to the reactor was recorded. The pressure was allowed to decrease, indicating a chemical reaction. When the pressure reached 0.69 bar (10 psi), the desired amount of ethylene oxide needed to complete a one-mole addition was added, or until the pressure reached 4.13 bar (60 psi). The pressure was continually allowed to decrease and ethylene oxide added until the pressure reached 4.13 bar (60 psi) until the desired amount of ethylene oxide was added and reacted.
- Once the desired amount of ethylene oxide was added and reacted, a 50 mL sample was taken under safe conditions. This retrieved aliquot was recorded and the amount of ethylene oxide needed for the next one mole addition of EO was calculated. On the pressure reaching 0.69 bar (10 psi) the desired amount of ethylene oxide needed to complete a one-mole addition was added, or until the pressure reached 60 psi. The pressure was allowed to decrease and the process was continued until the desired amount of ethylene oxide was added and consumed by the reaction. This same process was repeated until the entire ethylene oxide series was completed. The reaction mixture was removed from the Paar reactor. For each ethylene oxide sample, 5 g was submitted for NMR determination of actual ethylene oxide added.
- The rate of inversion in the following examples was measured using a qualitative analytical tool referred to as a "torque monitor." It consisted of a DC stir motor, a controller that can report the torque (DC voltage) required to maintain a constant stir speed, and a computer to record the torque reading as a function of time.
- All torque monitor tests were conducted at the 400-g scale in a 600-mL beaker in tap water from the city of Naperville, IL at room temperature (approximately 22°C) at the concentrations indicated unless otherwise noted. The solution was stirred at 300 rpm with a 2.54 × 7.62 cm (1" × 3") stainless-steel paddle positioned 1.27 cm (0.5 inch) from the bottom of the beaker and connected to the motor. Emulsion polymer was injected into the water vortex to start the experiment. Torque readings were collected every second and data worked-up in Microsoft Excel using a 20-period moving average.
- The percent inversion at 2 minute and 5 minute was estimated from 2 and 5 minute torque readings compared to the final torque readings.
- The activating surfactants used are listed in Table 2.
Table 2. Activating surfactants used in Example 4 Name Component 4OP-10eo 4-octyloxyphenol ethoxylate (9.9 ethylene oxide units) Activator # 1DOW TERGITOL NP-9.5 Activator # 2SASOL ALFONIC 1412-7 Activator # 3HUNTSMAN SURFONIC TDA-9 - A 50 mole% cationic polymer without activating surfactant was synthesized as follows.
- Monomer (aqueous) phase make-up: Into a 1-L beaker was added 227.7 g of a 49.5% aqueous acrylamide solution, 7.5 g adipic acid, 0.1 g sodium formate, and 52.5 g deionized water. The resulting components were stirred. To the resulting solution was added 0.13 g Versene 220 (tetrasodium ethylenediaminetetraacetate tetrahydrate available from Dow Chemical Company) and 384.1
g 80% DMAEA.MCQ (dimethylaminoethylacrylate methyl chloride quaternary salt) solution. The resulting mixture was stirred to produce a clear solution. - Oil phase preparation: Into a 2 L beaker was added 11.1 g sorbitan monooleate, 15.9 g SURFONIC L24-5 (a linear alcohol ethoxylate), and 270.0 g ISOPAR-M (a low odor, low aromatic hydrocarbon solvent of normal alkanes, isoalkanes, and cycloalkanes).
- Emulsion make-up: The oil phase components were mixed with an IKA ULTRA TURAX T-25 (fine head) homogenizer at 11,000 rpm for about one minute resulting in a homogenous surfactant solution. While stirring at 11,000 rpm, the monomer phase was added to the beaker over a 30-second period. The resulting emulsion was homogenized for an additional 85 seconds. The final emulsion (297 cP, #2 spindle-30 rpm) was charged into a 2 L reactor and cooled to 6.9°C.
- Polymerization: Polymerization was conducted under a nitrogen atmosphere. Initiation was accomplished by co-feeding 1.2 mL of a 1.2% sodium bromate solution at a rate between 0.79-2.78 mL/minute and 1 mL of a 0.58% sodium metabisulfite solution at a rate between 0.40-0.79 mL/minute in a manner that the temperature rise was about 1.5°C/min. At 34 min, the reaction temperature was 59.6°C, at which time the sodium bromate and sodium metabisulfite solution feed rates were held at 1.59 mL/minute and the reaction temperature controlled at 59.6°C. At one hour, the redox initiator feed stopped and 0.15 g of VAZO-64 was added to the reaction mixture to reduce the residual monomer. After an additional hour, the reaction mixture was cooled to room temperature yielding
emulsion polymer 1 with a viscosity of 403 cP (#2 spindle/30 rpm), a median particle diameter size of 0.56 µm, and an RSV of 19.8 dL/g. -
Polymer 1 blends with activatingsurfactants -
Polymer 1 blends with approximately 1.2% activator (Table 4) were obtained by adding the required amount of activator topolymer 1 blends containing approximately 1% activator.Polymer 1 blends with 1.4% activator were obtained similarly from thepolymer 1 activator blends containing 1.2% activator (Table 5). With each successive addition of activating surfactant, the resulting mixture was stirred for one hour and allowed to equilibrate for at least an additional two hours.Table 3. Polymer 1 blends with activating surfactants at approximately 1%Activator Weight Activator (g) Weight Emulsion 1 (g) Wt. Percent Activator (%) 4OP-10eo 0.3110 29.7030 1.036 Activator # 10.3086 29.7034 1.028 Activator # 20.3077 29.7047 1.025 Table 4. Polymer 1 blends with activating surfactants at approximately 1.2%Activator Wt. Remaining approximately 1% Polymer (g) Weight. Activator (g) Wt. Additional Activator (g) Wt. Percent Activator (%) 4OP-10eo 25.7620 0.2669 0.0468 1.216 Activator # 125.5478 0.2627 0.0484 1.215 Activator # 225.5864 0.2623 0.0475 1.209 Table 5. Polymer 1 blends with activating surfactants at approximately 1.4%Activator Wt. Remaining approximately 1.2% Polymer (g) Weight. Activator (g) Wt. Additional Activator (g) Wt. Percent Activator (%) 4OP-10eo 21.4471 0.2607 0.0450 1.422 Activator # 120.9415 0.2545 0.0415 1.411 Activator # 220.4074 0.2467 0.0418 1.411 -
Figure 1 depicts the inversion torque profile (0.5% invert) forpolymer 1 with approximately 1% activating surfactant. The rate of inversion forpolymer 1 with 4OP-10eo is faster than forpolymer 1 with eitheractivator -
Figure 2 depicts the inversion torque profile (0.5% invert) forpolymer 1 with approximately 1.2% activating surfactant. The rate of inversion forpolymer 1 with 4OP-10eo is faster than forpolymer 1 with eitheractivator -
Figure 3 depicts the inversion torque profile (0.5% invert) forpolymer 1 with approximately 1.4% activating surfactant. The rate of inversion forpolymer 1 with 4OP-10eo andactivator 1 are similar, but faster than forpolymer 1 withactivator 2. -
Figure 4 shows a comparison of the 2 minute percent inversion ofpolymer 1 with the activating surfactants. The percent inversion line is an average of two measurements (circles). The rate of inversion is faster forpolymer 1 with 4OP-1 0eo than forpolymer 1 with eitheractivator -
Figure 5 shows a comparison of the 5 minute percent inversion ofpolymer 1 with the activating surfactants. The percent inversion line is an average of two measurements (circles). The rate of inversion is faster forpolymer 1 with 4OP-10eo than forpolymer 1 with eitheractivator polymer 1 formulated with 1.2% 4OP-10eo at 5 minutes. - An un-activated 7:3 acrylamide/DADMAC (polydiallyldimethylammonium chloride) emulsion co-polymer (emulsion polymer 2) without an activating surfactant was used in this example.
-
Emulsion polymer 2 was weighed into a 118.3 ml (4 oz.) bottle.Polymer 2 activator blends with approximately 2%, approximately 2.5%, and approximately 3% activator were made by blending activator into the emulsion while stirring. The resulting blends were stirred for one hour and allowed to stand for at least two hours before testing.Table 6. Polymer 2 blends with activating surfactants at approximately 2%Activator Weight Emulsion 1 (g) Weight Activator (g) Wt. Percent Activator (%) 4OP-10eo 70.36 1.47 2.05 Activator # 177.82 1.62 2.04 Activator # 370.04 1.45 2.03 Table 7. Polymer 2 blends with activating surfactants at approximately 2.5%Activator Weight Emulsion 1 (g) Weight Activator (g) Wt. Percent Activator (%) 4OP-10eo 70.37 1.82 2.52 Activator # 171.78 1.82 2.47 Activator # 367.10 1.72 2.50 Table 8. Polymer 2 blends with activating surfactants at approximately 3%Activator Weight Emulsion 1 (g) Weight Activator (g) Wt. Percent Activator (%) 4OP-10eo 97.02 3.03 3.03 Activator # 197.01 3.14 3.14 Activator # 397.01 3.02 3.02 -
Figure 6 depicts the inversion torque profile (2% invert in DI water) forpolymer 2 with approximately 2% activating surfactant. The rate of inversion forpolymer 2 withactivator 1 is faster than forpolymer 2 with 4OP-1 0eo. Both are faster thanpolymer 2 activated withactivators -
Figure 7 depicts the inversion torque profile (2% invert in DI water) forpolymer 2 with approximately 2.5% activating surfactant. The inversion rates forpolymer 2 activated withactivator 1 and 4OP-10eo are similar. Both are faster thanpolymer 2 activated withactivators -
Figure 8 depicts the inversion torque profile (2% invert in DI water) forpolymer 2 with approximately 3% activating surfactant. The inversion rate forpolymer 2 withactivator 1 has the fastest rate of inversion. The rates of inversion forpolymer 2 withactivators 3 and 4OP-10eo are similar. All activated polymers invert faster thanpolymer 2 withactivator 2. -
Figure 9 shows a comparison of the 2 minute percent inversion ofpolymer 2 with activating surfactants. The 2 minute percent inversion forpolymer 2 withactivator 1 is greater than for the other polymers. The 2 minute percent inversion forpolymer 2 with 4OP-10eo is greater than forpolymer 2 withactivator 3 at 2, 2.5% activator concentration, but similar with 3% activator. -
Figure 10 shows a comparison of the 5 minute percent inversion ofpolymer 2 with activating surfactants. The 5 minute percent inversion forpolymer 2 withactivator 1 is greater than for the other polymers. The 5 minute percent inversion forpolymer 2 with 4OP-10eo is greater than forpolymer 2 withactivator 3. - Un-activated polyacrylamide emulsion polymer (emulsion polymer 3) without activating surfactant was used in this example.
-
Polymer 3 blends with approximately 1.8% activator (Table 10) were obtained by adding the required amount of activator topolymer 3 blends containing approximately 1.5 % activator (Table 9).Polymer 3 blends with 2.1 and 2.4 % activator were obtained similarly from thepolymer 3 activator blends containing 1.8% activator (Tables 11 and 12). With each successive addition of activating surfactant, the resulting mixture was stirred for an hour and allowed to equilibrate for at least an additional two hours.Table 9. Polymer 3 blends with activating surfactants at approximately 1.5%Activator Weight Emulsion 1 (g) Weight Activator (g) Wt. Percent Activator (%) 4OP-10eo 100.75 1.53 1.50 Activator # 1103.22 1.57 1.50 Activator # 2109.69 1.67 1.50 Activator # 3104.35 1.61 1.52 Table 10. Polymer 3 blends with activating surfactants at approximately 1.8%Activator Wt. Remaining approximately 1% Polymer (g) Weight. Activator (g) Wt. Additional Activator (g) Wt. Percent Activator (%) 4OP-10eo 81.04 1.21 0.27 1.82 Activator # 184.10 1.26 0.28 1.83 Activator # 290.69 1.35 0.29 1.81 Activator # 383.27 1.26 0.26 1.83 Table 11. Polymer 3 blends with activating surfactants at approximately 2.1%Activator Wt. Remaining approximately 1% Polymer (g) Weight. Activator (g) Wt. Additional Activator (g) Wt. Percent Activator (%) 4OP-10eo 62.28 1.13 0.19 2.12 Activator # 164.04 1.17 0.18 2.10 Activator # 272.65 1.32 0.21 2.10 Activator # 363.86 1.16 0.19 2.12 Table 12. Polymer 3 blends with activating surfactants at approximately 2.4%Activator Wt. Remaining approximately 1% Polymer (g) Weight. Activator (g) Wt. Additional Activator (g) Wt. Percent Activator (%) 4OP-10eo 43.16 0.91 0.13 2.42 Activator # 143.89 0.92 0.12 2.37 Activator # 254.23 1.13 0.18 2.42 Activator # 345.31 0.96 0.13 2.40 -
Figure 11 depicts the inversion torque profile (2% invert) forpolymer 3 with approximately 1.5% activating surfactant.Polymer 3 withactivator 1 outperformsactivator 3, which outperforms 4OP-10eo, which outperformsactivator 2. -
Figure 12 depicts the inversion torque profile (2% invert) forpolymer 3 with approximately 1.8% activating surfactant.Polymer 3 withactivator 1 performs similarly toactivator 3, which outperforms 4OP-10eo, which outperformsactivator 2. -
Figure 13 depicts the inversion torque profile (2% invert) forpolymer 3 with approximately 2.1% activating surfactant.Polymer 3 withactivator 1 outperforms 4OP-10eo, which outperformsactivator 3, which outperformsactivator 2. -
Figure 14 depicts the inversion torque profile (2% invert) forpolymer 3 with approximately 2.4% activating surfactant.Polymer 3 withactivator 1 outperforms 4OP-10eo, which outperformsactivator 3, which outperformsactivator 2. -
Figure 15 shows a comparison of the 2 minute percent inversion ofpolymer 3 with activating surfactants. The 2 minute percent inversion forpolymer 3 withactivator 1 is greater than for the other polymers. The 2 minute percent inversion forpolymer 3 with 4OP-10eo is greater than forpolymer 2 withactivators -
Figure 16 shows a comparison of the 5 minute percent inversion ofpolymer 3 with activating surfactants. The 5 minute percent inversion forpolymer 3 withactivator 1 is greater than for the other polymers. The 5 minute percent inversion forpolymer 3 with 4OP-10eo is less than forpolymer 3 withactivator 3 at 1.5 and 1.8% activating surfactant. The relative 5 minute percent inversion crosses, and at 2.1 and 2.4% activator polymer 3 with 4OP-1 0eo is greater than forpolymer 3 withactivator 3. - The inversion conditions employed in Examples 3a-3c (2.54 × 7.62 cm (1" × 3") paddle, 300 rpm) simulated inversion under "low shear" conditions. There is a benefit of having polymers that make-down efficiently under these conditions as this allows reduction of capital expenditures by use of less complex make-down equipment and elimination of inverted polymer aging tanks.
-
Polymer 1 was synthesized using a combination of sorbitan monooleate and a linear alcohol ethoxylate (7 eo) required 1.4% Activator # 3 to meet an inversion of greater than 90%. Unexpectedly forPolymer 1, thePolymer 1 blend with 4OP-1 0eo inverted better than the blends with the DOW TERGITOL NP-9.5 or the standard linear alcohol ethoxylate (Activator #2). At 5 minutes, full inversion was observed forPolymer 1 with 1.2% 4OP-1 0eo (Figure 5 ). -
Polymer 2 was formulated with 2.7% Activator # 2 to meet an inversion of greater than 90%. With 2.5% activating surfactant, the rate of inversion ofPolymer 2 with 4OP-1 0eo approached that ofPolymer 2 with TERGITOL NP-9.5 (Figure 7 ). Both of these activated polymers inverted better thanPolymer 2 with the linear alcohol ethoxylates (Activators 2 and 3). -
Polymer 3 was formulated with 2.35% Activator # 2 to meet an inversion of greater than 90%. As observed forPolymer 2, with 2.4% activating surfactant, the rate of inversion ofPolymer 3 with 4OP-10eo approached that ofPolymer 3 with Tergitol NP-9.5 (Figure 14 ). Both of these activated polymers inverted better thanPolymer 3 with the linear alcohol ethoxylates (Activators 2 and 3). - The performance of certain surfactants for inversion of anionic emulsion polymers was determined by torque monitor technique as described in Example 3, with some modifications described below.
- Torque monitor tests were conducted at the 500 g scale in a 1000-mL beaker in different waters (tap water from the City of Naperville, IL; synthetic sea water; high TDS brine) at room temperature (approximately 22°C) at the concentrations indicated in the examples unless otherwise noted. The solution was stirred at 400 rpm with a 1 an HS-1 6.73 cm (2.65 inch) indicage stirrer positioned 1.27 cm (0.5 inch) from the bottom of the beaker and connected to the motor. Emulsion polymer was injected into the water vortex to start the experiment. Torque readings were collected every second and data worked-up in Microsoft Excel using a 20-period moving average.
- The percent inversion at 2 minute and 5 minute was estimated from 2 and 5 minute torque readings compared to the final torque readings.
- The activating surfactants used are listed in Table 13.
Table 13. Activating surfactants used in Example 4 Name Component 4OP-nEO 4-octyloxyphenol ethoxylate (where n indicates moles of EO units) Activator # 1DOW TERGITOL NP-9.5 Activator # 2SASOL ALFONIC 1412 7 Activator # 3HUNTSMAN SURFONIC TDA-9 - Un-activated 7:3 acrylamide/acrylic acid emulsion co-polymer (emulsion polymer 4) without activating surfactant was used in this example.
-
Emulsion polymer 4 was weighed into a 29.57 ml (4 oz.) bottle.Polymer 4 activator blends with approximately 1.35% activator were made by blending activator into the emulsion while stirring. The resulting blends were stirred for one hour and allowed to stand for at least two hours before testing.Table 14. Polymer 4 blends with activating surfactants at approximately 1.35%Activator Weight Emulsion 4 (g) Weight Activator(g) Wt. Percent Activator (%) Activator # 174.012 1.013 1.35 % Activator # 2 74.098 1.018 1.36 % Activator # 3 74.008 1.020 1.35% 40P-10EO 74.912 1.016 1.34% 4OP-8.5EO 74.013 1.013 1.35% 4OP-7.2EO 74.121 1.012 1.35% -
Figure 17 depicts the inversion torque profile (0.5% invert in tap water) forpolymer 4 with approximately 1.35% activating surfactant. The inversion rates forpolymer 4 activated withactivator 1 and 4OP-7.2EO are similar.Polymer 4 blends with all 4OP-nEO activators are faster thanpolymer 4 activated withactivators -
Figure 18 shows a comparison of the 2 minute percent inversion ofpolymer 4 with activating surfactants. The 2 minute percent inversion forpolymer 4 with 4OP-7.2EO was greater than for the other polymers. -
Figure 19 shows a comparison of the 5 minute percent inversion ofpolymer 4 with activating surfactants. The 5 minute percent inversion forpolymer 4 with 4OP-7.2EO was greater than for the other polymers. - Un-activated 7:3 acrylamide/acrylic acid emulsion co-polymer (emulsion polymer 5) without activating surfactant was used in this example.
- Emulsion polymer 5 was weighed into a 118.3 ml (4 oz.) bottle.
Polymer 4 activator blends with approximately 2.5% activator were made by blending activator into the emulsion while stirring. The resulting blends were stirred for one hour and allowed to stand for at least two hours before testing.Table 15. Polymer 5 blends with activating surfactants at approximately 1.35% Activator Weight Emulsion 5 (g) Weight Activator(g) Wt. Percent Activator (%) Activator # 197.512 2.509 2.51 % Activator # 2 97.489 2.491 2.49 % Activator # 3 97.521 2.502 2.50% 4OP-8EO 97.591 2.507 2.50% 4OP-9EO 97.492 2.509 2.51% 4OP-10EO 97.511 2.501 2.50% - Preparation of Synthetic Sea Water (SSW): The 3.5% synthetic seawater used in the present Example was prepared by blending the components of Table 16. SSW was filtered through a
WHATMAN 1 filter by suction filtration to remove any particulate.Table 16. Ingredients of 3.5% SSW Reagent Amount (g) Sodium chloride (NaCl) 24.65 Calcium chloride CaCl2·2H2O 1.57 Magnesium chloride (MgCl2·6H2O) 11.39 Sodium bicarbonate (NaHCO3) 0.01 Sodium sulfate (Na2SO4) 4.38 Deionized water 957.99 -
Figure 20 depicts the inversion torque profile (1% invert in SSW) forpolymer 4 with approximately 2.5% activating surfactant. The rate of inversion for polymer 5 withactivator 1 was faster than for other polymers. The rate of inversion forpolymer 4 with activator 4OP-9EO was faster than polymer 5 withactivator 2 andactivator 3. -
Figure 21 shows a comparison of the 2 minute percent inversion of polymer 5 with activating surfactants. The 2 minute percent inversion for polymer 5 withactivator 1 was greater than for the other polymers. -
Figure 22 shows a comparison of the 5 minute percent inversion of polymer 5 with activating surfactants. The 5 minute percent inversion for polymer 5 withactivator 1 was greater than for the other polymers. - A 7.5:2.5 acrylamide/ATBS (acrylamido tertiary butyl sulfonic acid) emulsion co-polymer (emulsion polymer 6) without activating surfactant was used in this example.
-
Emulsion polymer 6 was weighed into a 118.3 ml (4 oz.) bottle.Polymer 4 activator blends with approximately 2.5% activator were made by blending activator into the emulsion while stirring. The resulting blends were stirred for one hour and allowed to stand for at least two hours before testing.Table 17. Polymer 6 blends with activating surfactants at approximately 2%Activator Weight Emulsion 4 (g) Weight Activator(g) Wt. Percent Activator (%) Activator # 198.011 2.013 2.01 % Activator # 2 98.107 2.028 2.03 % Activator # 3 98.197 2.012 2.01% 4OP-8EO 98.056 2.022 2.02% 4OP-9EO 98.151 2.028 2.02% 40P-10EO 98.101 1.9977 2.00% -
Figure 23 depicts the inversion torque profile (1% invert in SSW) forpolymer 6 with approximately 2.0% activating surfactant. The rate of inversion forpolymer 6 withactivator 1, 4OP-8EO and 4OP-9EO are similar.Polymer 6 blends with all 4OP-nEO activators are faster thanpolymer 4 withactivators activator 2 failed the torque test. -
Figure 24 shows a comparison of the 2 minute percent inversion ofpolymer 6 with activating surfactants. Thepolymer 6 blends with 4OP-8EO, 4OP-9EO, andactivator 1 invert fully in 2 minutes. -
Figure 25 shows a comparison of the 5 minute percent inversion ofpolymer 6 with activating surfactants. Thepolymer 6 blends with 4OP-8EO, 4OP-9EO, 4OP-10EO, andactivator 1 invert fully in 5 minutes. - The rate of inversion, or rate of viscosity build, was an important determinant of activity for anionic emulsion polymers used in upstream oil-recovery operations. Plots of torque versus time provided a way to evaluate the speed at which inversion took place. Field applications generally required that inversion occurred rapidly. The slope of the torque versus time curve in the early portion of the experiment was a good indicator of how rapidly inversion occurred. The torque typically levelled off to form a plateau region. Higher levels of torque in the plateau region indicated a higher emulsion viscosity.
- The results of Examples 4a-4c demonstrated that blends of anionic emulsion polymers comprising a 4-octyloxyphenol ethoxylate surfactant (with an appropriate moles of EO) provided improved performance over the blends of anionic emulsion polymers comprising an equivalent amount of linear alcohol ethoxylates (
Activators 2 and 3) in both fresh water and high TDS water. These data suggested that the surfactants can be substituted for linear alcohol ethoxylates (Activators 2 and 3) that are currently used as activator for anionic emulsion polymer formulations. - A standard 8:2 acrylamide/Acrylic acid emulsion co-polymer (emulsion polymer 7) without activating surfactant was used in this example. Anionic inverse emulsion polymers are used for friction reducing applications in oil and gas industries, more particularly during hydraulic fracturing to reduce pumping requirements. All evaluations with
polymer 7 blends were done using torque method, and flow-loop experiments (described below) in high (12.3%) TDS brine. A series of three experiments was conducted. - Preparation of High (12.3%) TDS Brine: The 12.3% TDS brine used in this example was formed by blending the components of Table 18. Brine was filtered through a
WHATMAN 1 filter by suction filtration to remove any particulate.Table 18. Ingredients of 12.3% TDS Brine Reagent Amount (g) NaCl 91.83 CaCl22H2O 21.60 MgCl2 6H2O 7.71 KCl 0.908 SrCl2 6H2O 1.179 DI water 876.77 - Invertability Comparison of
Polymer 7 Blends with 2.5 wt% surfactants with 4 wt% activator.Emulsion polymer 7 was weighed into a 118.3 ml (4 oz.) bottle.Polymer 7 activator blends with indicated percent activator were made by blending activator into the emulsion while stirring. The resulting blends were stirred for one hour and allowed to stand for at least two hours before testing.Table 19. Polymer 7 blends with activating surfactants at approximately 2.5-4%Activator Weight Emulsion 7 (g) Weight Activator(g) Wt. Percent Activator (%) 4OP-8EO 78.097 2.011 2.51% 4OP-9EO 78.191 2.023 2.52% 40P-10EO 78.009 1.997 2.50% 4OP-11EO 78.052 2.022 2.53% 40P-12EO 78.075 2.028 2.53% PR-9000 78.112 2.021 2.52% PR-9000 76.813 3.213 4.01% -
Figure 26 depicts the inversion torque profile (0.5% invert in 12.3% TDS brine) forpolymer 7 with approximately 2.5-4% activating surfactant. The rate of inversion forpolymer 6 with 2.5% 4OP-8EO and 4% activator 3 were similar. The rate of inversion was faster forpolymer 7 with all ethoxylated surfactants (4OP-nEO) than forpolymer 7 withactivator 3 at 2.5% (equivalent activator) concentrations. - Invertability Comparison of
Polymer 7 Blends with 1.5-3 wt% 4OP-8EO and 4wt% Activator 3 by Torque Measurements:Emulsion polymer 7 was weighed into a 118.3 ml (4 oz.) bottle.Polymer 7 activator blends with indicated percent activator were made by blending activator into the emulsion while stirring. The resulting blends were stirred for one hour and allowed to stand for at least two hours before testing.Table 17. Polymer 7 blends with activating surfactantsActivator Weight Emulsion 7 (g) Weight Activator (g) Wt. Percent Activator (%) 4OP-8EO 78.410 1.609 2.01% 4OP-8EO 78.107 2.003 2.50% 4OP-8EO 77.606 2.410 3.01% 4OP-8EO 78.812 1.211 1.51% PR-9000 76.804 3.211 4.01% -
Figure 27 depicts an inversion torque profile (0.5% invert in 12.3% TDS brine) forpolymer 7 with approximately 1.5-4% activators. The rate of inversion forpolymer 7 with 2.0%, 2.5%, and 3.0% 4OP-8EO and 4% activator 3 were comparable. -
Figure 28 shows a comparison of the 2 minute percent inversion ofpolymer 7 with activating surfactants. The 2 minute percent inversion forpolymer 7 with 4% activator 3 was greater than for the other polymers. -
Figure 29 shows a comparison of the 5 minute percent inversion ofpolymer 7 with activating surfactants. The 5 minute percent inversion forpolymer 7 with 4OP-7.2EO was greater than for the other polymers. - Friction Reduction Comparison of
Polymer 7 Blends with 1.5-3 wt% 4OP-8EO and 4wt% Activator 3 by Flow-Loop Experiments: Flow loop tests were conducted on a recirculating flow loop through 1.27 cm (0.5 inch) pipe (ID = 1.021 cm (0.402 inch)) at 8 gpm (Reynold's number = 6.3×104). A pressure drop was measured across a straight 4.83-1.47 m (4.83 feet) section of pipe. Friction reduction was calculated according toEquation 1 below. -
Figure 30 shows a comparison of the friction reduction properties ofpolymer 7 blends with 4% activator 3 and 1.5%, 2.0%, 2.5%, and 3.0% 4OP-8EO measured by flow loop tests in high TDS brine (13.4% TDS) at room temperature. -
Figure 31 shows a comparison of the friction reduction properties ofpolymer 7 blend with 4% activator 3 and 3.0% 4OP-8EO measured by flow loop tests in high TDS brine (13.4% TDS) at 40°F. - In the flow loop experiments done at room temperature,
polymer 7 blends with 4% Activator 3 and 3.0% 4OP-8EO showed similar friction reduction, i.e., about 70% friction reduction within one minute. In contrast, in the flow loop experiments done at lower temperature (40°F),polymer 7 blends with 3.0% 4OP-8EO showed better friction reduction (about 70% within two minutes) compared to 4% Activator 3 (about 60% within two minutes). - The results of this example show that the inversion and friction reducing performance of
polymer 7 blends with 4% SURFONIC TDA-9 was at least equivalent to that ofpolymer 7 blends with only 3% 4OP-8EO. - When introducing elements of the present invention or the preferred embodiments(s) thereof, the articles "a", "an", "the" and "said" are intended to mean that there are one or more of the elements. The terms "comprising", "including" and "having" are intended to be inclusive and mean that there may be additional elements other than the listed elements.
- In view of the above, it will be seen that the several objects of the invention are achieved and other advantageous results attained.
Claims (15)
- A polymer composition comprising:a water-in-oil emulsion comprising an aqueous phase comprising water and a water-soluble or water-dispersible polymer, and an oil phase comprising an oil and an emulsifying agent; andwhereinR3, R5, R9, and R10 are independently hydrogen or C1-C22 alkyl;R4 is C4-C30 alkyl;R6 is H, alkyl, or aryl;X is -O- or -NR8;R8 is hydrogen or C1-C4 alkyl;R11 is hydrogen, alkyl, alkylaryl, or aryl; andn is an integer from 1 to 20.
- The polymer composition of claim 1, wherein the water-in-oil emulsion further comprises the inversion surfactant having the structure of Formula 1; or further comprising an aqueous solution containing the inversion surfactant having the structure of Formula 1.
- A polymer composition comprising a water-soluble or water-dispersible polymer, an oil, a suspending agent, and
a surfactant having the structure of Formula 1:R3, R5, R9, and R10 are independently hydrogen or C1-C22 alkyl;R4 is C4-C30 alkyl;R6 is H, alkyl, or aryl;X is -O- or -NR8;R8 is hydrogen or C1-C4 alkyl;R11 is hydrogen, alkyl, alkylaryl, or aryl; andn is an integer from 1 to 20. - A method of dissolving the water-soluble or water-dispersible polymer of the polymer composition of any one of claims 1 to 3 comprising contacting the water-in-oil emulsion with the inversion surfactant having the structure of Formula 1.
- The method of claim 4, wherein the water-in-oil emulsion further comprises the inversion surfactant having the structure of Formula 1 and the water-in-oil emulsion is contacted with an aqueous solution; or wherein the water-in-oil emulsion is contacted with an aqueous solution comprising the inversion surfactant having the structure of Formula 1.
- Use of the inversion surfactant having the structure of Formula 1 for inverting the water-in-oil emulsion of the polymer composition of any one of claims 1 or 2.
- The polymer composition, use, or method of any one of claims 1 to 6, wherein R4 is C4-C16 alkyl; preferably, wherein R4 is C4-C12 alkyl; more preferably, wherein R4 is C8-C12 alkyl; most preferably, wherein R4 is octyl.
- The compound of claim 8, whereinR3, R5, R9, R10, and R11 are hydrogen;R4 is C8-C16 branched alkyl;X is -O- ; andn is an integer from 1 to 20.
- The polymer composition, method, use, or compound of any one of claims 1 to 8, wherein X is -O-.
- The polymer composition, method, use, or compound of any one of claims 1 to 10, wherein n is an integer from 2 to 20; preferably, wherein n is an integer from 4 to 16; more preferably, wherein n is an integer from 4 to 10.
- The polymer composition, method, use, or compound of any one of claims 1 to 11, wherein R3, R5, R9, and R10 are independently hydrogen or methyl; more preferably, wherein R3, R5, R9, and R10 are hydrogen.
- The polymer composition, method, use, or compound of any one of claims 1 to 12, wherein R6 is hydrogen, methyl, butyl, or benzyl; preferably, wherein R6 is methyl or wherein R6 is hydrogen.
- The polymer composition, method, use, or compound of any one of claims 1 to 13, wherein R11 is hydrogen or alkyl; preferably, wherein R11 is hydrogen or methyl; more preferably, wherein R11 is hydrogen.
- The polymer composition, use, or method of any one of claims 1 to 7 and 10 to 14,wherein the water-soluble or water-dispersible polymer comprises an anionic, a cationic, a nonionic, a zwitterionic, an amphoteric polymer, or a combination thereof; orwherein the water-soluble or water-dispersible polymer comprises a polyacrylamide, a polyacrylic acid, or a combination thereof; orwherein the inversion surfactant having the structure of Formula 1 has a concentration of from about 0.1 wt.% to about 10 wt.% based on the total weight of the emulsion; orwherein the inversion surfactant having the structure of Formula 1 has a concentration of from about 0.5 wt.% to about 5 wt.% based on the total weight of the emulsion; orwherein the polymer composition further comprises an ethoxylated C10-C16 alcohol; a C12-C13 primary alcohol of linear and mono-methyl branched alcohol having on average 9 moles ethylene oxide; an ethoxylate of a saturated C12-15 alcohol; an ethoxylated C12-14 alcohol; an ethoxylated primary branched saturated C13 alcohol; an ethoxylated C10 Guerbet alcohol; an ethoxylated saturated iso-C13 alcohol; a saturated, predominantly unbranched C13-15 oxo alcohol having 11 ethylene oxide groups; a secondary alcohol ethoxylate; a nonionic, alkoxylated alcohol; a polyoxyethylene (9) synthetic primary C13/C15 alcohol; an isotridecyl alcohol ethoxylated with an average of 9 moles ethylene oxide; an ethoxylated linear primary C12-14 alcohol; an ethoxylated nonylphenol; tert-octylphenoxypoly(ethoxyethanol); a tridecyl ether phosphate; a polyoxyethylene (5) soyaallylamine; a polyethylene glycol (PEG) 400 monooleate; a PEG 600 monooleate; aPEG-25 castor oil; a PEG-30 castor oil; a PEG-40 castor oil; an aliphatic phosphate ester with 10 moles EO; an aliphatic phosphate ester with 6 moles EO; an oleic acid monoethanol amide with 14 moles ethylene oxide; a soyamine ethoxylate; or a combination thereof; orwherein the inversion surfactant is activated by contacting the inversion surfactant with an aqueous solution; orwherein the inversion surfactant is activated by contacting the inversion surfactant with an inversion aid, wherein the inversion aid comprises glycol, a polypropylene glycol, polyglycerol, urea, sorbitol, sucrose, glycerol, a polyglycerol, a phosphate, choline chlorine, guanidine, dioctyl-sulfosuccinate, malic acid, lactic acid, N-(phosphonomethyl)glycine, 2-phosphonopropanoic acid, 3-phosphonopropanoic acid, 4-phosphonobutanoic acid, a phosphinosuccinic oligomer, a polyethylene glycol, urea, sorbitol, sucrose, glycerol, a phosphate, choline chlorine, , or a combination thereof.
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US201762611264P | 2017-12-28 | 2017-12-28 | |
PCT/US2018/066785 WO2019133432A1 (en) | 2017-12-28 | 2018-12-20 | Surfactant compositions and uses as inverters |
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US11473004B2 (en) | 2016-12-02 | 2022-10-18 | University Of Wyoming | Microemulsions and uses thereof to displace oil in heterogeneous porous media |
WO2020191279A1 (en) * | 2019-03-21 | 2020-09-24 | Rhodia Operations | Friction reducers |
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2018
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- 2018-12-20 WO PCT/US2018/066785 patent/WO2019133432A1/en unknown
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US11167257B2 (en) | 2021-11-09 |
US20190201858A1 (en) | 2019-07-04 |
WO2019133432A1 (en) | 2019-07-04 |
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